CN103998414B - Liquid-repellant compound, polymkeric substance, composition, article and manufacture method thereof - Google Patents

Liquid-repellant compound, polymkeric substance, composition, article and manufacture method thereof Download PDF

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Publication number
CN103998414B
CN103998414B CN201280061108.0A CN201280061108A CN103998414B CN 103998414 B CN103998414 B CN 103998414B CN 201280061108 A CN201280061108 A CN 201280061108A CN 103998414 B CN103998414 B CN 103998414B
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China
Prior art keywords
compound
repellant
liquid
polymkeric substance
cured film
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Expired - Fee Related
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CN201280061108.0A
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Chinese (zh)
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CN103998414A (en
Inventor
伊藤昌宏
鹤冈薰
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AGC Inc
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Asahi Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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Abstract

The invention provides a kind of solidification compound and having makes this solidification compound solidify and the article of cured film that obtain and manufacture method thereof, even if this solidification compound can form the cured film with liquid-repellant that the ultraviolet of good more than the illumination wavelength 300nm of insulativity, liquid-repellant also can be lyophilised fully.The present invention uses this solidification compound to form cured film, and this solidification compound comprises the liquid-repellant polymkeric substance of the unit (u1) with the liquid-repellant compound represented based on following formula (m1).[changing 1] wherein, Cf is the fluoro-alkyl between the fluoro-alkyl of carbon number 1 ~ 20 or carbon atom with the carbon number 1 ~ 20 of etheric oxygen atom; R 1and R 2it is separately the alkyl or phenyl of hydrogen atom, carbon number 1 ~ 6; X is Sauerstoffatom, sulphur atom, nitrogen-atoms or NH; N is the integer of 0 ~ 4; M is 1 when X is Sauerstoffatom, sulphur atom or NH, is 2 when X is nitrogen-atoms; Z is R 4r 5c=CR 3-CO-; R 3, R 4and R 5be separately hydrogen atom or methyl.

Description

Liquid-repellant compound, polymkeric substance, composition, article and manufacture method thereof
Technical field
The present invention relates to a kind of liquid-repellant compound lyophilised by uviolizing, liquid-repellant polymkeric substance, solidification compound, coating composition and there is the article of cured film, the article with the pattern in lyophily region and liquid-repellant region and manufacture method thereof.
Background technology
In fields such as semiconductor element, indicating meter, luminous elements, several functions film is practical.Functional film is the film material configuration with desired characteristic obtained in desired location and by its patterning.Such as, in field of thin film transistors, propose manufacture method as described below: form the cured film with liquid-repellant at substrate surface, to this cured film surface partly irradiation ultraviolet radiation to make illuminated ultraviolet part lyophilised, make composition for electrodes be optionally attached to cured film through lyophilised part, thus formed electrode.The method, compared with the method based on photoetching, is the method that can form the electrode of required pattern with less operation easily, just receives publicity.
As forming the material with the cured film of liquid-repellant lyophilised by uviolizing, such as, propose following material.
(1) material (with reference to patent documentation 1) of photocatalyst (titanium dioxide etc.) and tackiness agent (organopolysiloxane etc.) is comprised.
(2) comprise decompose by uviolizing, the composition (with reference to patent documentation 2) of the low-molecular-weight fluorochemicals that removes.
(3) side chain has the polyimide (with reference to patent documentation 3) of hydrophobic group.
(4) main chain has the polyimide (with reference to patent documentation 4) of thiolic acid ester bond.
Prior art document
Patent documentation
Patent documentation 1: endorsement of patent No. 4300012 publication
Patent documentation 2: No. 2005/054256th, International Publication
Patent documentation 3: Japanese Patent Laid-Open 2005-310962 publication
Patent documentation 4: No. 2008/133300th, International Publication
Summary of the invention
Invent technical problem to be solved
When having the cured film of liquid-repellant with the material formation of above-mentioned (1), photocatalyst still remains in this cured film.When the article with functional film are thin film transistor, semiconductor element etc., cured film is insulating film, and therefore remaining in insulating film photocatalyst can cause detrimentally affect to the characteristic of insulating film (insulativity etc.).
In addition, when there is the cured film of liquid-repellant with the composition formation comprising fluorochemicals of above-mentioned (2), because the molecular weight of fluorochemicals is lower, so fluorochemicals is evenly dispersed in this cured film, fluorochemicals can not be present in the surface (opposition side of base material) of cured film more.Therefore, the liquid-repellant on cured film surface is not enough sometimes.In addition, the insulation characterisitic of the cured film of gained is not enough sometimes.
Further, when having the cured film of liquid-repellant with the polyimide formation of above-mentioned (3) and (4), polyimide can absorb the ultraviolet (ultraviolet of such as more than wavelength 300nm) of longer wavelength side.Therefore, when using high voltage mercury lamp (i line 365nm), YAG laser (3 times of ripple 355nm) etc. to be commonly used for the light source of ultraviolet light source, sensitivity is not enough.In addition, the material that specific inductivity is lower compared with polyimide is sometimes required recently.
The object of this invention is to provide a kind of liquid-repellant compound and liquid-repellant polymkeric substance and solidification compound and coating composition, the liquid-repellant of this liquid-repellant compound and liquid-repellant polymkeric substance is good, decomposed in molecule by the uviolizing of more than wavelength 300nm, decomposition residue containing Cf base can depart from, even if this solidification compound and coating composition can form the cured film with liquid-repellant that the ultraviolet of good more than the illumination wavelength 300nm of insulativity and liquid-repellant also can be lyophilised fully.
In addition, the object of this invention is to provide a kind of there is insulativity and the good cured film of liquid-repellant article and insulativity good and there is article and the manufacture method thereof of the pattern in lyophily region and liquid-repellant region.
The technical scheme that technical solution problem adopts
The present invention is liquid-repellant compound, liquid-repellant polymkeric substance, solidification compound, the coating composition of the formation with following [1] ~ [15] and has the article of cured film, the article with the pattern in lyophily region and liquid-repellant region and manufacture method thereof.
[1] the liquid-repellant compound that represents of following formula (m1);
[changing 1]
Wherein, Cf is the fluoro-alkyl between the fluoro-alkyl of carbon number 1 ~ 20 or carbon atom with the carbon number 1 ~ 20 of etheric oxygen atom; R 1and R 2it is separately the alkyl or phenyl of hydrogen atom, carbon number 1 ~ 6; X is Sauerstoffatom, sulphur atom, nitrogen-atoms or NH; N is the integer of 0 ~ 4; M is 1 when X is Sauerstoffatom, sulphur atom or NH, is 2 when X is nitrogen-atoms; Z is R 4r 5c=CR 3-CO-; R 3, R 4and R 5be separately hydrogen atom or methyl.
[2] liquid-repellant polymkeric substance, it has the unit (u1) based on the liquid-repellant compound described in above-mentioned [1].
[3] the liquid-repellant polymkeric substance described in above-mentioned [2], it also comprises and has cross-linking functional group and not containing the unit (u2) of Cf base.
[4] solidification compound, it comprises above-mentioned [2] or the liquid-repellant polymkeric substance described in [3].
[5] solidification compound described in above-mentioned [4], it also comprises radical polymerization initiator (D).
[6] above-mentioned [4] or the solidification compound described in [5], it also comprises the fluorine-containing polyarylene prepolymer (A) with cross-linking functional group.
[7] solidification compound described in above-mentioned [6], it also comprises, and number-average molecular weight is 140 ~ 5000, the compound (B) with cross-linking functional group, non-contain fluorine atoms.
[8] solidification compound according to any one of above-mentioned [4] ~ [7], wherein, described fluorine-containing polyarylene prepolymer (A) be make to have cross-linking functional group and phenolic hydroxyl group compound (x1) and there is either one or both in the compound (x2) of cross-linking functional group and fluorine atom substituted aroma ring, compound (y) that following formula (y) represents, the compound (z) with more than 3 phenolic hydroxyl group under the existence of dehydrohalogenating agent, carry out condensation reaction and obtain, the prepolymer with cross-linking functional group and ehter bond;
[changing 2]
Wherein, a is the integer of 0 ~ 3, and b is the integer of 0 ~ 3, and c is the integer of 0 ~ 3; Rf 1and Rf 2be separately the fluoro-alkyl of carbon number less than 8, the F in aromatic nucleus represents that the hydrogen atom of this aromatic nucleus is all replaced by fluorine atoms.
[9] coating composition, it comprises solidification compound according to any one of above-mentioned [4] ~ [8] and solvent (E).
[10] article, its cured film that there is base material and at substrate surface, the solidification compound according to any one of above-mentioned [4] ~ [8] is solidified and obtain.
[11] article, it is the article on cured film surface with the pattern in lyophily region and liquid-repellant region, and wherein, the cured film that this liquid-repellant region is solidified by the solidification compound made according to any one of above-mentioned [4] ~ [8] and obtained is formed.
[12] have the manufacture method of the article of the pattern in lyophily region and liquid-repellant region on cured film surface, it comprises following operation (I) ~ (II):
(I) be coated with coating composition according to claim 9 at substrate surface, except desolventizing (E), carry out heating or rayed and form the operation of cured film;
(II) to described cured film surface irradiation ultraviolet radiation partly, the operation on cured film surface with the article of the pattern in lyophily region and liquid-repellant region is obtained.
The manufacture method of the article [13] described in above-mentioned [12], wherein, also comprises following operation (III) after described operation (II):
(III) optionally adhere in described lyophily region surface more than one that be selected from composition for electrodes, semiconductor layer composition, conductor layer composition, transistor material composition and resin layer composition, form more than one the operation being selected from electrode, semiconductor layer, conductor layer, transistor material and resin layer.
[14] article described in above-mentioned [10], wherein, are also formed with in described lyophily region surface more than one that be selected from electrode, semiconductor layer, conductor layer, transistor material and resin layer.
[15] article described in above-mentioned [14], it is thin film transistor.
The effect of invention
By the present invention, a kind of liquid-repellant compound and liquid-repellant polymkeric substance can be provided, also can provide a kind of solidification compound and coating composition, the liquid-repellant of this liquid-repellant compound and liquid-repellant polymkeric substance is good, decomposed in molecule by the uviolizing of more than wavelength 300nm, decomposition residue containing Cf base can depart from, even if this solidification compound and coating composition can form the cured film with liquid-repellant that the ultraviolet of good more than the illumination wavelength 300nm of insulativity and liquid-repellant also can be lyophilised fully.
In addition, by the present invention, a kind of article with insulativity and the good cured film of liquid-repellant can be provided, a kind of insulativity also can be provided good and there is the article of the pattern in lyophily region and liquid-repellant region and the efficient manufacture method of these article.
Accompanying drawing explanation
Fig. 1 is the sectional view of the example representing OTFT.
Fig. 2 is the sectional view of an example of the manufacturing process representing OTFT.
Fig. 3 is the sectional view of an example of the manufacturing process representing OTFT.
Embodiment
In this specification sheets, the compound that formula (m1) represents is denoted as compound (m1).So record too with the compound that other formulas represent.
In this specification sheets, " liquid-repellant " refers to the general name of water repellency and oil repellent.
In this specification sheets, " lyophily " refers to wetting ability and oil loving general name.
In this specification sheets, " lyophilised " refers to that liquid-repellant relatively becomes lyophily, specifically refers to diminish with the contact angle of water or organic solvent.
In this specification sheets, " fluoro-alkyl " refers to part or all group be replaced by fluorine atoms of the hydrogen atom of alkyl; " perfluoroalkyl " refers to the group that the hydrogen atom of alkyl has all been replaced by fluorine atoms.
In this specification sheets, " methacryloyl (oxygen) base " refers to the general name of methacryloyl and methacryloxy." acryloyl (oxygen) base " too.
In this specification sheets, " (methyl) acryl " refers to the general name of acryl and methacryloyl." (methyl) acryloxy " too.
In this specification sheets, " unit " refers to the unit deriving from this monomer formed by the polymerization of monomer.Unit both can be by being polymerized the unit directly formed, and also can be a part for this unit has been changed into the unit of other structure by processing polymkeric substance.
In this specification sheets, " monomer " refers to the compound with the functional group can be polymerized under the effect of free radical.
In this specification sheets, " cross-linking functional group " refers to the functional group can be polymerized under the effect of free radical.
As cross-linking functional group, can exemplify the carbon-to-carbon unsaturated double-bond that can be polymerized under the effect of free radical, the unsaturated triple bond of carbon-to-carbon that can be polymerized under the effect of free radical, can open loop under the effect of free radical ring, comprise these group etc.Unsaturated double-bond and unsaturated triple bond both may reside in the inside (being also denoted as internal alkene type below) of molecular chain, also may reside in the end (being also denoted as terminal olefin type below) of molecule, high from the viewpoint of reactivity, preferred terminal olefin type.Internal alkene type also comprises the situation that there is unsaturated double-bond as cyclenes hydro carbons in a part for aliphatics ring.As the cross-linking functional group of terminal olefin type, the alkenyl of preferred carbon number less than 4, the alkynyl of carbon number less than 4.
As cross-linking functional group; specifically can exemplified by vinyl, allyl group, pseudoallyl, 3-butenyl, methacryloyl, methacryloxy, acryl, acryloxy, vinyloxy group, allyloxy, trifluoro vinyl, trifluoro-ethylene oxygen base, ethynyl, 1-oxo ring penta-2,5-diene-3-base, cyano group, alkoxysilane group, diaryl methylol, hydroxyl fluorenyl, cyclobutene ring (シ Network ロ Block タ レ ン Ring), oxyethane ring.
High from the viewpoint of reactivity, easily obtain the high cured film of cross-linking density; as cross-linking functional group, be preferably selected from more than one cross-linking functional group of vinyl, allyl group, ethynyl, vinyloxy group, allyloxy, acryl, acryloxy, methacryloyl and methacryloxy.
Number-average molecular weight (Mn) in this specification sheets uses the known polystyrene standard sample of molecular weight to make calibration curve, uses this calibration curve to be undertaken measuring by gel permeation chromatography and the polystyrene conversion molecular weight that obtains.
[liquid-repellant compound]
Liquid-repellant compound of the present invention is compound (m1).
[changing 3]
Cf is the fluoro-alkyl between the fluoro-alkyl of carbon number 1 ~ 20 or carbon atom with the carbon number 1 ~ 20 of etheric oxygen atom.
Excellent and good with the intermiscibility of other monomer from the viewpoint of liquid-repellant, the carbon number of Cf base is preferably 2 ~ 20, is more preferably 2 ~ 15, is particularly preferably 4 ~ 8.In addition, low from the viewpoint of environmental pressure, the carbon number of Cf base is preferably less than 6, is more preferably 2 ~ 6, is particularly preferably 4 ~ 6.
In Cf base, more good from the viewpoint of the liquid-repellant on cured film surface, relative to the sum of fluorine atom and hydrogen atom, the quantity of fluorine atom is preferably more than 80%, be particularly preferably 100%, that is, Cf base particularly preferably has the perfluoroalkyl of the carbon number 1 ~ 20 of etheric oxygen atom between the perfluoroalkyl of carbon number 1 ~ 20 or carbon atom.
Cf base can be straight-chain, also can be branch-like.
As Cf base, specifically-CF can be exemplified 3,-CF 2cF 3,-CF (CF 3) 2,-CH (CF 3) 2,-CF 2cHF 2,-(CF 2) 2cF 3,-(CF 2) 3cF 3,-(CF 2) 4cF 3,-(CF 2) 5cF 3,-(CF 2) 6cF 3,-(CF 2) 7cF 3,-(CF 2) 8cF 3,-(CF 2) 9cF 3,-(CF 2) 11cF 3,-(CF 2) 15cF 3,-CF (CF 3) O (CF 2) 5cF 3,-CF 2oCF 2cF 2oCF 2cF 3,-CF 2o (CF 2cF 2o) pcF 3(wherein, p is the integer of 1 ~ 8) ,-CF (CF 3) O (CF 2cF (CF 3) O) qc 6f 13(wherein, q is the integer of 1 ~ 4) ,-CF (CF 3) O (CF 2cF (CF 3) O) rc 3f 7(wherein, r is the integer of 0 ~ 5).
R 1and R 2be separately the alkyl or phenyl of hydrogen atom, carbon number 1 ~ 6, from the viewpoint of by uviolizing, easily depart from containing the decomposition residue of Cf base, preferred R 1and R 2in at least one party be not hydrogen atom, more preferably R 1and R 2both sides are not hydrogen atom, particularly preferably R 1and R 2both sides are methyl.
X is Sauerstoffatom, sulphur atom, nitrogen-atoms or NH, from the viewpoint of easily manufacturing liquid-repellant polymkeric substance (C) (liquid-repellant polymkeric substance (C) not easily gelation), preferred Sauerstoffatom, sulphur atom, NH, from the viewpoint of easily obtaining raw material, particularly preferably Sauerstoffatom.
M is 1 when X is Sauerstoffatom, sulphur atom or NH, is 2 when X is nitrogen-atoms, from the viewpoint of easily manufacturing liquid-repellant polymkeric substance (C) (liquid-repellant polymkeric substance (C) not easily gelation), is preferably 1.
Here, liquid-repellant polymkeric substance (C) refers to the liquid-repellant polymkeric substance of the unit (u1) had based on liquid-repellant compound (m1).
N is the integer of 0 ~ 4, from the viewpoint of the acquisition complexity of raw material and the simplicity of synthesis, is preferably the integer of 0 ~ 2, is particularly preferably the integer of 0 ~ 1.
Z is R 4r 5c=CR 3-CO-.
R 3, R 4and R 5be separately hydrogen atom or methyl, high from the viewpoint of reactivity, preferred hydrogen atom.That is, as the preferred acryl of Z.
(manufacture method of compound (m1))
As the manufacture method of compound (m1), the method for carrying out the reaction represented with following formula can be exemplified.By the HO-in compound (a1) left side under the existence of tertiary amine with compound (b1) optionally esterification and after obtaining compound (c1) ,-OH on the right side of compound (c1) is obtained compound (m1) with compound (d1) esterification.
[changing 4]
R 1and R 2for methyl, X be Sauerstoffatom, n be the compound of 1 when, compound (a1) manufactures by the manufacture method of " 4-(2-hydroxyl-oxethyl) the phenyl 2-hydroxyl-2-propyl group ketone " recorded in Japanese Patent Laid-Open No. Sho 62-81345 publication.As commercially available product, IRGACURE2959 (ProductName, Ciba Specialty Chemicals (チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ society) makes) etc. can be exemplified.
[liquid-repellant polymkeric substance]
Liquid-repellant polymkeric substance of the present invention is the liquid-repellant polymkeric substance (being also denoted as below " liquid-repellant polymkeric substance (C) ") of the unit (being also denoted as below " unit (u1) ") had based on liquid-repellant compound of the present invention.
From the viewpoint of the hardness, solvent resistance etc. of water repellency film, liquid-repellant polymkeric substance (C) has cross-linking functional group and the unit (being also denoted as below " unit (u2) ") not containing Cf base preferred also comprising.
Liquid-repellant polymkeric substance (C) can have other unit (u3) beyond unit (u1) and unit (u2).
Unit (u1) in liquid-repellant polymkeric substance (C), unit (u2), other unit (u3) both can be combined into random shape, also can be combined into block-wise.
The Oil repellent of liquid-repellant polymkeric substance (C) is preferably 5 ~ 70 quality %, is more preferably 5 ~ 60 quality %, is particularly preferably 8 ~ 60 quality %.If Oil repellent is more than the lower value of above-mentioned scope, then the liquid-repellant on cured film surface is more good.If below the higher limit of above-mentioned scope, then the adaptation between cured film and the layer be adjacent is good.
The number-average molecular weight (Mn) of liquid-repellant polymkeric substance (C) is preferably 1000 ~ 50000, is particularly preferably 3000 ~ 20000.Number-average molecular weight (Mn) is if more than the lower value of above-mentioned scope, then liquid-repellant polymkeric substance (C) moves fully on cured film surface, therefore can embody more good liquid-repellant.If below the higher limit of above-mentioned scope, then good with the intermiscibility of the prepolymer (A) in solidification compound, flawless cured film can be formed.
(unit (u1))
Unit (u1) is the unit deriving from the compound (m1) formed by the polymerization of compound (m1).Carbon-to-carbon unsaturated double-bond in the Z base (group of the same race with cross-linking functional group) of compound (m1) loses by being polymerized, because this element (u1) does not have cross-linking functional group.
The ratio of the unit (u1) in liquid-repellant polymkeric substance (C) is preferably 10 ~ 90 quality %, is more preferably 15 ~ 90 quality %, is more preferably 20 ~ 90 quality % further, be particularly preferably 30 ~ 90 quality %.Unit (u1) if ratio more than the lower value of above-mentioned scope, then the liquid-repellant on cured film surface is more good.If below the higher limit of above-mentioned scope, then liquid-repellant polymkeric substance (C) is easily dissolved in the solvent (E) of coating composition.
(unit (u2))
Unit (u2) is the unit having cross-linking functional group and do not contain Cf base.
The cross-linking functional group of unit (u2) and following fluorine-containing polyarylene prepolymer (hereinafter also referred to " prepolymer (A) ") and the cross-linking functional group of compound (B) react, become to be integrated with them, form the cured film of high, the excellent solvent resistance of hardness.
From the viewpoint of the acquisition complexity of raw material and the simplicity of synthesis, the quantity of the cross-linking functional group in unit (u2) is preferably 1.
As the cross-linking functional group in unit (u2), high from the viewpoint of the reactivity of the cross-linking functional group with prepolymer (A) and compound (B), preferably (methyl) acryloyl (oxygen) base.
The cross-linking functional group of cross-linking functional group that coexist in solidification compound, compound (B) and liquid-repellant polymkeric substance (C) can be the same or different.
Polymerizable functional group's (group of the same race with cross-linking functional group) that monomer has loses by being polymerized, and the cross-linking functional group because of this element (u2) is not the polymerizable functional group that monomer has.Therefore, the cross-linking functional group in this multipolymer is introduced after monomer polymerization is normally obtained multipolymer by the cross-linking functional group of unit (u2), by modification etc.
The cross-linking functional group of unit (u2) introduces with the various method of modifying that the compound with cross-linking functional group reacts preferably by making the multipolymer with reactive functional groups.As this method of modifying, can suitably adopt known method.Method specifically as described below: make that there is the compound (m4) of polymerizable functional group and reactive functional groups and compound (m1) copolymerization, after obtaining that there is the multipolymer containing the unit (u4) of reactive functional groups, react with the compound (a2) with functional group and the cross-linking functional group reacted with the reactive functional groups of unit (u4), obtain the liquid-repellant polymkeric substance (C) with unit (u2).Unit (c2) is the bonding of unit (u4) and the compound (a2) formed by the polymerization by compound (m4) and the unit generated.
As reactive functional groups, hydroxyl, epoxy group(ing), carboxyl etc. can be exemplified.When reactive functional groups is hydroxyl, the functional group of reacting with reactive functional groups can exemplify carboxyl, isocyanate group, acyl chlorides etc.When reactive functional groups is epoxy group(ing), the functional group of reacting with reactive functional groups can exemplify carboxyl etc.When reactive functional groups is carboxyl, the functional group of reacting with reactive functional groups can exemplify hydroxyl, epoxy group(ing) etc.
As concrete method of modifying, such as following method (i) ~ (vi) can be exemplified.
I () makes to have the monomer copolymerization of hydroxyl and the multipolymer that obtains and the method for anhydride reaction with cross-linking functional group.
(ii) monomer copolymerization of hydroxyl and method that the multipolymer that obtains reacts with the compound with isocyanate group and cross-linking functional group is made to have.
(iii) monomer copolymerization of hydroxyl and method that the multipolymer that obtains reacts with the compound with acid chloride group and cross-linking functional group is made to have.
(iv) anhydride copolymers of polymerizable functional group and method that the multipolymer that obtains reacts with the compound with hydroxyl and cross-linking functional group is made to have.
V () makes to have the monomer copolymerization of carboxyl and method that the multipolymer that obtains reacts with the compound with epoxy group(ing) and cross-linking functional group.
(vi) monomer copolymerization of epoxy group(ing) and method that the multipolymer that obtains reacts with the compound with carboxyl and cross-linking functional group is made to have.
Make to have the multipolymer of unit (u4) and compound (a2) when reacting, both can make the reactive functional groups total overall reaction of multipolymer, a part for the reactive functional groups of multipolymer also can be made to react.When the latter, the liquid-repellant polymkeric substance (C) of gained has the unit (u4) deriving from compound (m4).
The liquid-repellant polymkeric substance (C) used in solidification compound also can have unit (u4).In addition, when the reactive functional groups of unit (u4) may bring bad impact to solidification compound, the functional group that the reactive functional groups of unit (u4) and having also can be made to react with this reactive functional groups and the compound (b2) without cross-linking functional group react, thus reactive functional groups is changed into inertia group.
As compound (b2), such as ethyl isocyanate can be exemplified, propyl isocyanate, n-Isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, hexyl isocyanate, NSC 87419, isocyanic acid dodecyl ester, isocyanic acid stearyl, phenylcarbimide, Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, isobutyryl chloride, pivalyl chloride, isoveryl chloride, valeryl chloride, 3, 3-dimethyl-butyrylchlorine, caproyl chloride, oenanthyl chloro, 2-ethyl hexanoyl chloro, capryl(yl)chloride, pelargonyl chloride, decanoyl chloride, lauroyl chloride, preferred ethyl isocyanate, propyl isocyanate, Acetyl Chloride 98Min. and propionyl chloride.
Unit reactive functional groups having been changed into inertia group is called unit (u5).
As compound (m4), (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-4-hydroxybutyl etc. can be exemplified in method (i), (ii) and (iii).Maleic anhydride, itaconic anhydride, citraconic anhydride, Tetra hydro Phthalic anhydride etc. can be exemplified in method (iv).(methyl) vinylformic acid etc. can be exemplified in method (v).(methyl) glycidyl acrylate, 3,4-epoxycyclohexyl-methyl acrylate etc. can be exemplified in method (vi).
As compound (a2), maleic anhydride, itaconic anhydride, citraconic anhydride, Tetra hydro Phthalic anhydride etc. can be exemplified in method (i).2-(methyl) acryloyloxyethyl isocyanate, 1,1-two (acryloyloxymethyl) ethyl isocyanates etc. can be exemplified in method (ii).(methyl) acrylate chloride, 3-crotonyl chloride etc. can be exemplified in method (iii).(methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-4-hydroxybutyl etc. can be exemplified in method (iv).(methyl) glycidyl acrylate, 3,4-epoxycyclohexyl-methyl acrylate etc. can be exemplified in method (v).(methyl) vinylformic acid etc. can be exemplified in method (vi).
As unit (u2), the unit that the unit preferably making to derive from the monomer with hydroxyl react with the compound with isocyanate group and cross-linking functional group and obtains, or the unit that the unit making to derive from the monomer with hydroxyl and the compound with acid chloride group and cross-linking functional group react and obtain.The unit that the unit particularly preferably making to derive from more than one the monomer being selected from (methyl) 2-Hydroxy ethyl acrylate and (methyl) vinylformic acid-4-hydroxybutyl reacts with more than one the compound being selected from (methyl) acrylate chloride, 2-methacryloxyethyl isocyanic ester and 2-acryloyloxyethyl isocyanate and formed.Good with the reactivity of prepolymer (A).
(unit (u3))
Liquid-repellant polymkeric substance (C) can have other unit (u3) beyond unit (u1) and unit (u2) as required in the scope not damaging the effect improving liquid-repellant.When liquid-repellant polymkeric substance (C) has unit (u4) or unit (u5), these unit regard as unit (u3).
Unit (u3) is introduced in liquid-repellant polymkeric substance (C) preferably by making the compound (m3) with polymerizable functional group be polymerized.In addition, the compound (a3) with the functional group of reacting with the reactive functional groups of liquid-repellant polymkeric substance (C) is also preferably made to react and introduce in multipolymer.
As compound (a3), such as ethyl isocyanate can be exemplified, propyl isocyanate, n-Isopropyl isocyanate, butyl isocyanate, tert-butyl isocyanate, hexyl isocyanate, NSC 87419, isocyanic acid dodecyl ester, isocyanic acid stearyl, phenylcarbimide, Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, isobutyryl chloride, pivalyl chloride, isoveryl chloride, valeryl chloride, 3, 3-dimethyl-butyrylchlorine, caproyl chloride, oenanthyl chloro, 2-ethyl hexanoyl chloro, capryl(yl)chloride, pelargonyl chloride, decanoyl chloride, lauroyl chloride, preferred ethyl isocyanate, propyl isocyanate, Acetyl Chloride 98Min. and propionyl chloride.
As the compound (m3) of providing unit (u3), except compound (m4), the fluorochemical monomer etc. beyond hydrocarbon system olefines, vinyl ethers, pseudoallyl ethers, allyl ether series, vinyl ester, allyl ester class, (methyl) esters of acrylic acid, (methyl) acrylic amide, aromatic ethenyl compound, chloro-alkenes class, conjugated diene, compound (m1) can be exemplified.Compound (m3) can have reactive functional groups.As this reactive functional groups, hydroxyl, carbonyl, alkoxyl group etc. can be exemplified.Compound (m3) can be used alone a kind, also can two or more also use.
As the concrete example of compound (m3), can exemplified by acrylic, methacrylic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid-3-methylbutyl butenoate, the just own ester of (methyl) vinylformic acid, (methyl) acrylic acid-2-ethyl-just own ester, (methyl) n-octyl, (methyl) acrylate cyclohexyl, (methyl) isobornyl acrylate, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (1,1-dimethyl-3-oxo butyl) (methyl) acrylate, 2-acetoacetoxyethyl (methyl) acrylate, 2-methoxy ethyl (methyl) acrylate, 2-ethoxyethyl group (methyl) acrylate, (methyl) acrylamide, N-vinyl acetamide, N-vinyl formamide, N-(1,1-dimethyl-3-oxo butyl) (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, two (methoxymethyl) (methyl) acrylamide of N, N-, vinylbenzene, RUVA-93 (Otsuka Chemical Co., Ltd system) etc.From the viewpoint of acquisition complexity, preferred vinylformic acid, methacrylic acid, (methyl) methyl acrylate, (methyl) n-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) n-octyl, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, RUVA-93.
The ratio of the unit (u2) in liquid-repellant polymkeric substance (C) is preferably 5 ~ 90 quality %, is more preferably 5 ~ 85 quality %, is more preferably 5 ~ 80 quality % further, be particularly preferably 5 ~ 60 quality %, most preferably be 5 ~ 50 quality %.Unit (u2) if ratio more than the lower value of above-mentioned scope, then good with the reaction of prepolymer (A) and compound (B).If below the higher limit of above-mentioned scope, then the liquid-repellant on cured film surface is more good.
The ratio of the unit (u3) in liquid-repellant polymkeric substance (C) is preferably below 70 quality %, is more preferably below 60 quality %, is particularly preferably below 50 quality %.As lower value, be preferably 0 quality %.Unit (u3) if ratio below the higher limit of above-mentioned scope, then can guarantee the sufficient ratio of unit (u1) and unit (u2), the liquid-repellant on cured film surface and the solidified nature of solidification compound can not be damaged.
When liquid-repellant polymkeric substance (C) is made up of unit (u1) and unit (u2), the content of preferred cell (u1) is the amount of Oil repellent in above-mentioned preferable range made in liquid-repellant polymkeric substance (C), and rest part is unit (u2).
When liquid-repellant polymkeric substance (C) is made up of unit (u1), unit (u2) and unit (u3), the content of preferred cell (u1) is the amount of Oil repellent in above-mentioned preferable range made in liquid-repellant polymkeric substance (C), unit (u3) is in the scope of above-mentioned preferred ratio, and rest part is unit (u2).
(manufacture method of liquid-repellant polymkeric substance (C))
Liquid-repellant polymkeric substance (C) is by obtaining multipolymer, carrying out above-mentioned modification to manufacture as required by monomer polymerization.
The polymerization of monomer is preferably carried out in a solvent.In addition, in the polymerization of monomer, preferably polymerization starter is used, preferably usage chain transfer agent as required.When the preservation of monomer, preferably use stopper as required.
As solvent, alcohols (ethanol can be exemplified, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, ethylene glycol etc.), ketone (acetone, 2-butanone, methyl iso-butyl ketone (MIBK), pimelinketone etc.), cellosolve class (2-methyl cellosolve, cellosolvo, butoxy ethanol etc.), Trivalin SF class (2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) ethanol, 2-(2-Butoxyethoxy) ethanol etc.), ester class (methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, glycol diacetate, glycerol triacetate etc.), ethers (diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether etc.) etc.Solvent can be used alone a kind, also can two or more also use.
As polymerization starter, known organo-peroxide, inorganic peroxide, azo-compound etc. can be exemplified.Organo-peroxide and inorganic peroxide also can combine with reductive agent and use as redox class catalyzer.Polymerization starter can be used alone a kind, also can two or more also use.
As organo-peroxide, benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, t-butyl hydroperoxide, tert-butyl peroxide-α-isopropyl benzene etc. can be exemplified.
As inorganic peroxide, ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide, percarbonate etc. can be exemplified.
As azo-compound, can 2 be exemplified, 2 '-Diisopropyl azodicarboxylate, 1,1 '-azo two (hexamethylene-1-nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo-bis-iso-dimethyl, 2,2 '-azo two (2-amidine propane) dihydrochloride etc.
As chain-transfer agent, known thio-alcohol, haloalkane base class etc. can be exemplified.Chain-transfer agent can be used alone a kind, also can two or more also use.
As thio-alcohol, n-butyl mercaptan, n-dodecane mercaptan, tert.-butyl mercaptan, ethyl thioglycolate, thioglycollic acid-2-ethyl hexyl ester, 2 mercapto ethanol etc. can be exemplified.
As haloalkane base class, chloroform, tetracol phenixin, carbon tetrabromide etc. can be exemplified.
As stopper, known stopper can be exemplified.
As the concrete example of stopper, 2,6 ditertiary butyl p cresol etc. can be exemplified.
Also solvent similar to the above can be used by time copolymer-modified.But, the solvent that may react with compound (a2) had better not be used.The polymerization of monomer can be carried out in a solvent, continues to add compound (a2) and makes it react, thus obtain polymkeric substance (C).
The modification of multipolymer can be carried out under the existence of catalyzer and neutralizing agent.Such as, when the multipolymer making to have hydroxyl reacts with the compound with isocyanate group and cross-linking functional group, tin compound etc. can be used as catalyzer.
As tin compound, dibutyl tin dilaurate, two (maleic mono-ester) two fourth tin, the pungent tin of tin dilaurate two, two (maleic mono-ester) two pungent tin, oxalic acid two fourth tin etc. can be exemplified.Tin compound can be used alone a kind, also can two or more also use.
When the multipolymer with hydroxyl is reacted with the compound with acid chloride group and cross-linking functional group, basic catalyst can be used.
As basic catalyst, triethylamine, pyridine, xylidine, tetramethyl-urea etc. can be exemplified.Basic catalyst can be used alone a kind, also can two or more also use.
Liquid-repellant polymkeric substance (C) of the present invention comprises the unit (u1) based on liquid-repellant compound.Because liquid-repellant compound has Cf base, so the liquid-repellant of this liquid-repellant compound and liquid-repellant polymkeric substance (C) is good.Therefore, make to comprise the solidification compound solidification of liquid-repellant polymkeric substance (C) and the surfaces repel water of cured film that obtains and oil, even and if water and wet goods temporarily adhere to and also can easily dirt settling be removed from surface.Dirt settling is not limited to liquid, also can be the solid with tack surface.
Liquid-repellant polymkeric substance (C) has to give reducing makes solidification compound solidify and the characteristic of tack on the cured film surface that obtain and being easy to the character of the characteristic of dirt settling removing.Liquid-repellant polymkeric substance (C) is useful as the non-tack imparting agent mixed in solidification compound.Such as, when cured film surface has the oily matters such as sebum (particularly fingerprint etc.) to adhere to, dirt settling easily can be removed.When utilizing this characteristic, also can be formed as described above the surface that its characteristic local reduces.
In addition, this liquid-repellant compound records the R in " copolymerizable light trigger " in Japanese Patent Laid-Open No. Sho 62-81345 publication 3be substituted by the compound (m1) of Cf base, therefore same with " the copolymerizable light trigger " recorded in this publication, even if there is not photocatalyst etc., the uviolizing also by wavelength 350 ~ 370nm is decomposed in molecule, and the decomposition residue containing Cf base can depart from.That is, liquid-repellant polymkeric substance (C) is by uviolizing, and the Cf base that side chain exists easily departs from.Therefore, by the cured film surface irradiation ultraviolet radiation partly obtained making the solidification compound comprising liquid-repellant polymkeric substance (C) solidify, the liquid-repellant of the illuminated ultraviolet part on cured film surface can be made to reduce, and is lyophily relative to the part of non-irradiation ultraviolet radiation.
As described below, surperficial across the figuratum photomask irradiation ultraviolet radiation of tool by the cured film obtained making the solidification compound comprising liquid-repellant polymkeric substance (C) solidify, the part of non-irradiation ultraviolet radiation can be made lyophilised, become the surface of the pattern with not illuminated ultraviolet liquid-repellant region and lyophily region.
[solidification compound]
Solidification compound of the present invention is the composition comprising liquid-repellant polymkeric substance (C).
As described below, be by making solidification compound thermofixation of the present invention or photocuring and the film that forms of the cured article obtained.Therefore, solidification compound of the present invention is the composition of Thermocurable or the composition of light solidified.
Solidification compound of the present invention, from the viewpoint of solidified nature, preferably also comprises radical polymerization initiator (D).From the viewpoint of the solvent resistance, specific inductivity etc. of cured film, preferably also comprise the solidification compound of prepolymer (A).From the viewpoint of the hardness of cured film, preferably go back inclusion compound (B).
(fluorine-containing polyarylene prepolymer (A))
Fluorine-containing polyarylene prepolymer (A) has the polyarylene structure of multiple aromatic ring through singly-bound or linking group bonding, has fluorine atom simultaneously, and has cross-linking functional group.By making solidification compound comprise prepolymer (A), the specific inductivity of cured film can be reduced.
The cross-linking functional group of prepolymer (A) does not react in fact when the manufacture of prepolymer (A), but under the existence of radical polymerization initiator (D), by giving external energy generation Raolical polymerizable, cause the intermolecular crosslinked or chain extension of prepolymer (A).
In addition, think that it also reacts with the cross-linking functional group of compound (B) and liquid-repellant polymkeric substance (C), they become be integrated and form cured film.Good from the viewpoint of low, under the existence of radical polymerization initiator (D) the reactivity of reactivity when manufacturing prepolymer (A), as the cross-linking functional group in prepolymer (A), particularly preferably vinyl, ethynyl.
As the linking group in polyarylene structure, ehter bond (-O-), thioether bond (-S-), carbonyl (-CO-), alkylsulfonyl (-SO can be exemplified 2-) etc.In prepolymer (A), have between aromatic ring and be called " fluorine-containing poly (arylene ether) prepolymer " by the prepolymer of the structure of the linking group bonding containing ehter bond (-O-).This fluorine-containing poly (arylene ether) prepolymer is owing to having etheric oxygen atom, and therefore molecular structure has flexibility, and the flexibility of cured film is good, is preferred.
As prepolymer (A), preferably comprise fluorine-containing poly (arylene ether) prepolymer, be particularly preferably only made up of fluorine-containing poly (arylene ether) prepolymer.
Contain the concrete example of the linking group of ehter bond as this, the ehter bond (-O-), the alkylidene group etc. containing etheric oxygen atom in carbochain that are only made up of etheric oxygen atom can be exemplified.
Prepolymer (A) has fluorine atom.If have fluorine atom, then the specific inductivity of cured film and dielectric loss easily reduce, therefore ideal as the material forming insulating film.If the specific inductivity of insulating film and dielectric loss low, then can suppress the delay of signal velocity, obtain the element of electrical characteristic excellences.
In addition, if have fluorine atom, then the water-intake rate of cured film reduces, and therefore the wiring part of bonding electrodes and periphery thereof can suppressed to grade the change this point or excellent in rotten (getting rusty) this point that can suppress metal of engagement state at place.Be very effective in this point is improved in the reliability of element.
As the concrete example of prepolymer of the present invention (A), either one or both in the compound (x1) making there is cross-linking functional group and phenolic hydroxyl group and the compound (x2) with cross-linking functional group and fluorine atom substituted aroma ring can be exemplified, compound (y) that following formula (y) represents, the compound (z) with more than 3 phenolic hydroxyl group under the existence of dehydrohalogenating agent, carry out condensation reaction and obtain, the prepolymer (hereinafter also referred to " prepolymer (A1) ") with cross-linking functional group and ehter bond.
[changing 5]
Wherein, a is the integer of 0 ~ 3, and b is the integer of 0 ~ 3, and c is the integer of 0 ~ 3;
Rf 1and Rf 2be separately the fluoro-alkyl of carbon number less than 8, the F in aromatic nucleus represents that the hydrogen atom of this aromatic nucleus is all replaced by fluorine atoms.
As the preference of compound (y), can exemplify that a is 0 or 1, b is 0 or 1, c is 0 or 1, Rf 1for CF 3, Rf 2for CF 3compound etc., wherein preferably perfluor benzene, perfluorotoluene, perfluorinated biphenyl.
As compound (z), such as 1 can be exemplified, 3,5-trihydroxybenzene, three (4-hydroxy phenyl) methane, three (4-hydroxy phenyl) ethane, 4-[4-[1, two (4-hydroxy phenyl) ethyl of 1-]]-alpha, alpha-dimethylbenzyl phenol, preferably 1,3,5-trihydroxybenzene and three (4-hydroxy phenyl) ethane.
Prepolymer (A1) has the compound (z) of the phenolic hydroxyl group of more than 3 by using, branched structure is introduced in polymer chain, by molecular structure three-dimensional, thus the free volume of polymkeric substance is made to increase and realize low density, i.e. low-k.
In addition, easily there is the accumulation of aromatic nucleus and the orientation of molecule that causes in the straight chain polymer generally with aromatic nucleus, and cured article of the present invention is inhibited due to the orientation introducing branched structure and molecule, and thus double refraction diminishes.
Prepolymer (A1) manufactures by either one or both in the method for following (i) or (ii).
I () makes compound (y), compound (z), compound (x1) under the existence of dehydrohalogenating agent, carry out the method for condensation reaction.
(ii) make compound (y), compound (z), compound (x2) under the existence of dehydrohalogenating agent, carry out the method for condensation reaction.
When manufacturing prepolymer (A1) by the both sides of above-mentioned (i) and (ii), compound (y), compound (z), compound (x1) and compound (x2) is made to carry out condensation reaction under the existence of dehydrohalogenating agent.
For any one of the method for above-mentioned (i) or (ii), condensation reaction can one-phase total overall reaction, also the multistage can be divided to react.In addition, can make to make other compound react again after specific compound preferential reaction in reaction raw materials.When condensation reaction divides the multistage to carry out, the intermediate product obtained in way can for follow-up reaction (condensation reaction) after reaction system separation and purification.Starting compound can be put in reacting environment quickly, also drops into serially or drops into off and on.
In the manufacture method of above-mentioned prepolymer (A1), shown in the reaction that condensation reaction represents as shown in the formula (1), the carbon atom being combined with fluorine atom of compound (y) is attacked by the phenoxy group derived by phenolic hydroxyl group, then the fluorine atom reaction mechanism etc. of sloughing, generates ehter bond.
In addition, when compound (z) and/or (x1) have 2 phenolic hydroxyl group of ortho relationship, by same reaction mechanism etc., there is generation two in the reaction represented by following formula (2) the possibility of alkene (ジ オ キ シ Application) skeleton.From the viewpoint of molecular structure have flexibility, cured film flexibility good, preferably do not have two the prepolymer (A1) of alkene skeleton.That is, compound (z) and/or (x1) preferably do not have 2 phenolic hydroxyl group of ortho relationship.
[changing 6]
[changing 7]
As the compound (x1) used in manufacture method (i), preferably there is the compound (x11) of 1 phenolic hydroxyl group and there is the compound (x12) of 2 phenolic hydroxyl group.
As the concrete example of compound (x11), the phenols that 4-Vinyl phenol etc. has reactive double bond can be exemplified, the acetylenylbenzene phenols such as 3-ethynyl phenol, 4-phenylene-ethynylene phenol, 4-(4-fluorophenyl) ethynyl phenol.They may be used alone, can also be two or more kinds in combination.
As the concrete example of compound (x12), can 2 be exemplified, 2 '-bis-(phenylene-ethynylene)-5,5 '-dihydroxybiphenyl, 2, two (phenylene-ethynylene) dihydroxybiphenyl class such as 2 '-bis-(phenylene-ethynylene)-4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxyl tolane, 3, the dihydroxydiphenyl acetylene classes etc. such as 3 '-dihydroxyl tolane.They may be used alone, can also be two or more kinds in combination.
As the compound (x2) used in manufacture method (ii), preferably there is the compound of cross-linking functional group and the perfluor such as perfluorophenyl, perfluorinated biphenyl aromatic nucleus.As concrete example, pentafluorostyrene can be exemplified, vinylformic acid PFBBR ester, methacrylic acid PFBBR ester, vinylformic acid pentafluorophenyl group ester, methacrylic acid pentafluorophenyl group ester, perfluoro styrene, pentafluorophenyl group trifluoro vinyl ether, the fluoro-1-propylene of 3-(pentafluorophenyl group) five etc. have reactive double bond containing fluoro aryl class, five fluorine benzonitriles etc. have cyano group containing fluoro aryl class, pentafluorophenyl group acetylene, the fluorine-containing aryl ethane classes such as nine fluorine diphenylethyne, phenylene-ethynylene penta fluoro benzene, phenylene-ethynylene nine fluorine biphenyl, the fluorine-containing diaryl acetylenes such as ten fluorine tolane.They may be used alone, can also be two or more kinds in combination.
Because crosslinking reaction is carried out and the raising of the thermotolerance of the prepolymer cures thing of gained at a lower temperature, as compound (Y-2), it is better the fluorine-containing aryl ethane class containing fluoro aryl class, there is triple bond with double bond.
As dehydrohalogenating agent used during manufacture prepolymer (A1), be better basic cpd, particularly preferably alkali-metal carbonate, supercarbonate or oxyhydroxide.As concrete example, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide etc. can be exemplified.
For the usage quantity of dehydrohalogenating agent, in manufacture method (i), relative to the total mole number of compound (z) with the phenolic hydroxyl group of compound (x1), needing the amount of more than 1 times with molar ratio computing, is better 1.1 ~ 3 times.In manufacture method (ii), relative to the mole number of the phenolic hydroxyl group of compound (z), needing the amount of more than 1 times with molar ratio computing, is better 1.1 ~ 3 times.
Described manufacture method (i) is with in (ii), and condensation reaction is better carry out in polar solvent.As polar solvent, be better the amidess such as N,N-dimethylacetamide, DMF, N-Methyl pyrrolidone, the sulfoxide types such as methyl-sulphoxide, the sulfone classes such as tetramethylene sulfone, ether, tetrahydrofuran (THF), two the polar solvent of the aprotic such as ethers such as alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, TRIGLYME.
Not making the decreased solubility of the prepolymer of generation (A1), not producing condensation reaction in dysgenic scope, toluene, dimethylbenzene, benzene, tetrahydrofuran (THF), phenylfluoroform, hexafluoro dimethylbenzene etc. in polar solvent, can be comprised.By containing these materials, the polarity (specific inductivity) of solvent changes, and can control speed of response.
Condensation reaction condition is better at 10 ~ 200 DEG C 1 ~ 80 hour.At being more preferably 20 ~ 180 DEG C 2 ~ 60 hours, particularly preferably at 50 ~ 160 DEG C 3 ~ 24 hours.
In manufacture method (i), the usage quantity of compound (z) is better 0.1 ~ 1 times with the molar ratio computing relative to compound (y), particularly preferably 0.3 ~ 0.6 times.The usage quantity of compound (x1) is better 0.1 ~ 2 times with the molar ratio computing relative to compound (y), particularly preferably 0.2 ~ 1.5 times.
In manufacture method (ii), the usage quantity of compound (z) is better 0.5 ~ 2 times with the molar ratio computing relative to compound (y), is more preferably 0.6 ~ 1.5 times.The usage quantity of compound (x2) is better 0.1 ~ 2 times with the molar ratio computing relative to compound (y), particularly preferably 0.2 ~ 1.5 times.
If the usage quantity of each compound is within the scope of this, then the prepolymer (A1) of gained has low dielectric constant values and high heat resistance concurrently, so be preferred.
The manufacture method of prepolymer (A1) can according to the solvent resistance of the cured article of gained after solidification, suitably select manufacture method (i) or (ii) than physical property such as specific inductivity, double refraction, flexibilities.Such as, when using manufacture method (ii), there is the ratio specific inductivity that solidifies the cured article obtained and the general lower tendency of birefringence value in manufactured prepolymer (A1).That is, in order to obtain than specific inductivity and the low cured article of birefringence value, be better manufacture prepolymer (A1) by manufacture method (ii).
During prepolymer (A1) passes through after condensation reaction or solubilisate and, redeposition, extraction, the method purifying such as filtration.When purifying carries out under the state of depositing the polar solvent preferably adopted during fabrication or the state being dissolved or dispersed in solvent described later (E), efficiency is good, so be preferred.
As the insulating film in various electronic component and multilayer wired in insulating film purposes in, deriving from the reason that the metals such as the potassium of dehydrohalogenating agent, sodium and free halogen atom may become the corrosion causing the bad and distribution of the action of transistor etc., is therefore better purifying fully.
As the suitable example of prepolymer (A1), can exemplify and make aromatic fluorine compound (perfluor (1,3,5-triphenylbenzene), perfluorinated biphenyl etc.), phenolic compound (1,3,5-trihydroxybenzene, 1,1,1-tri-(4-hydroxy phenyl) ethane etc.), react under the existence of dehydrohalogenating agent (salt of wormwood etc.) and the polymkeric substance obtained containing the aromatics (pentafluorostyrene, acetoxy-styrene, 1-chloro-4-methyl-benzene, pentafluorophenyl group acetylene etc.) of cross-linking functional group.
The number-average molecular weight (Mn) of prepolymer (A) is preferably 1000 ~ 100000, is particularly preferably 5000 ~ 50000.Number-average molecular weight (Mn) is if more than the lower value of above-mentioned scope, then the flexibility of cured film is not easy to reduce.If below the higher limit of above-mentioned scope, then the purifying of solidification compound is easy.
The content of the prepolymer (A) in solidification compound of the present invention is preferably 10 ~ 99.99 quality %, is more preferably 20 ~ 99.95 quality %, is more preferably 30 ~ 70 quality % further, be particularly preferably 50 ~ 70 quality %.If more than the lower value of above-mentioned scope, then the specific inductivity of cured film fully reduces.If below the higher limit of above-mentioned scope, then easily solidify at low temperatures, therefore the solvent resistance of cured film can fully improve.
When solidification compound inclusion compound (B), the content of prepolymer (A) is preferably 20 ~ 90 mass parts in the total (100 mass parts) of prepolymer (A) and compound (B), be more preferably 30 ~ 85 mass parts, be particularly preferably 40 ~ 80 mass parts.
(compound (B))
Compound (B) is number-average molecular weight (Mn) is 140 ~ 5000, has cross-linking functional group and does not have the compound of fluorine atom.By making solidification compound inclusion compound (B), the cured film that hardness is high can be formed.
The number-average molecular weight (Mn) of compound (B) is preferably 200 ~ 3000, is particularly preferably 250 ~ 2500.Number-average molecular weight (Mn) is if more than the lower value of above-mentioned scope, then compound (B) not easily volatilizees because of heating.If below the higher limit of above-mentioned scope, then the viscosity of compound (B) is suppressed must be lower, easily obtains uniform solidification compound when mixing with prepolymer (A).
From the viewpoint of can by intermolecular cross-linking, the cross-linking functional group of compound (B) be preferably more than 2, is more preferably 2 ~ 20, is particularly preferably 2 ~ 8.
The cross-linking functional group of compound (B) is preferably not contain fluorine atoms, with the cross-linking functional group of prepolymer (A), the group that reacts in the same operation of the operation of Raolical polymerizable is occurring.
The cross-linking functional group of compound (B) at least reacts and causes crosslinked or chain extension between cross-linking functional group.In addition, think that the cross-linking functional group of it and prepolymer (A) and liquid-repellant polymkeric substance (C) reacts, their become be integrated and form cured film.
As the cross-linking functional group of compound (B), high from the viewpoint of reactivity, easy acquisition, preferably (methyl) acryloyl (oxygen) base, higher from the viewpoint of reactivity, particularly preferably acryloyl (oxygen) base.In addition, cross-linking functional group can have two or more in 1 molecule.
Prepolymer (A), compound (B) and liquid-repellant polymkeric substance (C) can have two or more cross-linking functional group respectively in 1 molecule.In addition, the cross-linking functional group in the prepolymer (A) coexisted in solidification compound, compound (B) and liquid-repellant polymkeric substance (C) can be the same or different.
As the concrete example of compound (B), Dipentaerythritol triacrylate three (undecane acid esters) can be exemplified, Dipentaerythritol Pentaacrylate list undecane acid esters, ethoxylation isocyanuric acid triacrylate, 6-caprolactone modification three-(2-acryloyl-oxyethyl) isocyanuric acid ester, two [4-(2-acryloyloxyethoxy) phenyl] fluorenes of 9,9-, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, polypropyleneglycol diacrylate, polypropylene glycol dimethacrylate, epoxidation bisphenol a diacrylate, epoxidation bisphenol a dimethacrylate, propoxylated bisphenol diacrylate, propoxylated bisphenol dimethacrylate, decamethylene-glycol diacrylate, 1,6 hexanediol diacrylate, HDDMA, BDO dimethacrylate, 1,3 butylene glycol dimethacrylate, hydroxyl trimethylacetic acid neopentylglycol diacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, pentaerythritol triacrylate, Viscoat 295, ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295, triallylcyanurate, cyanacrylate, trimethyl allyl isocyanuric acid ester, BDO divinyl ether, 1,9-nonanediol divinyl ether, cyclohexanedimethanol divinyl base ether, triethyleneglycol divinylether, trimethylolpropane tris vinyl ether, tetramethylolmethane tetravinyl ether, vinylformic acid-2-(2-vinyloxyethoxy) ethyl ester, methacrylic acid-2-(2-vinyloxyethoxy) ethyl ester, trimethylolpropane allyl ether, pentaerythritol triallyl ether, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, ethoxylation tetramethylol methane tetraacrylate shown in following formula (B-1), propoxylated pentaerithytol tetraacrylate shown in following formula (B-2), two (TriMethylolPropane(TMP)) tetraacrylate, Tricyclodecane Dimethanol diacrylate, Tricyclodecane Dimethanol methacrylic ester, compound etc. shown in following formula (B-3).
[changing 8]
As compound (B), also polyester acrylate (compound that two ends modifying the condenses of dibasic alcohol and diprotic acid with vinylformic acid obtain: Toagosei Co., Ltd (East Asia synthesizes society) system can be used, ProductName: ア ロ ニ ッ Network ス (M-6100, M-6200, M-6250, M-6500); The compound that the C-terminal modifying the condenses of polyvalent alcohol and polyprotonic acid with vinylformic acid obtains: Toagosei Co., Ltd's system, ProductName: ア ロ ニ ッ Network ス (M-7100, M-7300K, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050)).These can obtain as commercially available product.
Consider from acquisition complexity and reactive viewpoint, as the compound used in the present invention (B), preferred ethoxylation isocyanuric acid triacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, Viscoat 295, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, two (TriMethylolPropane(TMP)) tetraacrylate, Tricyclodecane Dimethanol diacrylate, 6-caprolactone modification three-(2-acryloyl-oxyethyl) isocyanuric acid ester.
When in solidification compound of the present invention containing compound (B), its content is preferably 10 ~ 80 mass parts in the total (100 mass parts) of prepolymer (A) and compound (B), be more preferably 15 ~ 70 mass parts, be particularly preferably 20 ~ 60 mass parts.If content more than the lower value of above-mentioned scope, then easily solidifies at low temperatures, therefore the solvent resistance of cured film fully improves.Go for the low temperature process of the low base material of use thermotolerance.In addition, when base material is big area, the warpage of base material can be prevented.If below the higher limit of above-mentioned scope, then the specific inductivity of cured film fully reduces.
(liquid-repellant polymkeric substance (C))
Liquid-repellant polymkeric substance (C) is the liquid-repellant polymkeric substance of the invention described above.By making to comprise liquid-repellant polymkeric substance (C) in solidification compound, the liquid-repellant on cured film surface is good.
The content of the liquid-repellant polymkeric substance (C) in solidification compound of the present invention is preferably 0.01 ~ 20 quality %, is more preferably 0.05 ~ 10 quality %, is particularly preferably 0.1 ~ 5 quality %.If content is more than the lower value of above-mentioned scope, then the liquid-repellant on cured film surface is good.If below the higher limit of above-mentioned scope, then the film physical property of cured film is good.
When in solidification compound of the present invention containing prepolymer (A) and compound (B), the content of liquid-repellant polymkeric substance (C) is relative to the total (100 mass parts) of prepolymer (A) and compound (B), be preferably 0.1 ~ 20 mass parts, be particularly preferably 0.2 ~ 15 mass parts.
(radical polymerization initiator (D))
Solidification compound of the present invention can be Thermocurable also can be light solidified.During for Thermocurable, better make to contain thermal polymerization (D1) in solidification compound as radical polymerization initiator (D), during for light solidified, be better make it contain Photoepolymerizationinitiater initiater (D2) as radical polymerization initiator (D).
The solidification compound of light solidified can be used as the photosensitive material of minus.
As thermal polymerization (D1), known thermal polymerization can be used.As concrete example, can 2 be exemplified, 2 '-Diisopropyl azodicarboxylate, benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide etc.From the viewpoint of decomposition temperature, preferably 2,2 '-Diisopropyl azodicarboxylate, benzoyl peroxide.Thermal polymerization (D1) can be used alone a kind, also can two or more also use.
When in solidification compound of the present invention containing thermal polymerization (D1), its content is preferably 0.1 ~ 20 quality %, is particularly preferably 1 ~ 15 quality %.If content more than the lower value of above-mentioned scope, then easily solidifies at low temperatures, therefore the solvent resistance of cured film fully improves.If below the higher limit of above-mentioned scope, then the storage stability of solidification compound is good.
As Photoepolymerizationinitiater initiater (D2), known Photoepolymerizationinitiater initiater can be used.As concrete example, oxime ester derivative (1 can be exemplified, 2-acetyl caproyl, 1-[4-(phenyl)-, 2-(o-benzoyl oxime)] (such as Inc. of Ciba Specialty Chemicals, ProductName: IRGACUREOXE01), ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(o-acetyl-oxime) (such as Inc. of Ciba Specialty Chemicals, ProductName: IRGACUREOXE02) etc.), the alpha-aminoalkyl benzophenone compounds (ProductName of Inc. of Ciba Specialty Chemicals: IRGACURE369, ProductName: IRGACURE907 etc.), acylphosphine oxide compounds (Inc. of Ciba Specialty Chemicals, ProductName: DAROCURTPO etc.) etc.Consider from reactive viewpoint of the free radical produced, preferred IRGACUREOXE01, IRGACUREOXE02.
When in solidification compound of the present invention containing Photoepolymerizationinitiater initiater (D2), its content is preferably 0.1 ~ 20 quality %, is particularly preferably 1 ~ 15 quality %.If content more than the lower value of above-mentioned scope, then easily solidifies at low temperatures, therefore the solvent resistance of cured film fully improves.If below the higher limit of above-mentioned scope, then the storage stability of solidification compound is good.
(additive)
As required, in the scope not damaging effect of the present invention, can mix in solidification compound and be selected from stablizer class (UV light absorber, antioxidant, solar heat protection polymerizing agent etc.), surfactant-based (levelling agent, defoamer, antisettling agent, dispersion agent etc.), softening agent, tackifier etc. are at the additive of the known various additive of coating applications.
Cured film is not removed in manufacturing process way and in the final product as when playing material (such as interlayer dielectric etc.) that the parts of function remain, can adds cementability rising agent (silane coupling agent etc.) in curing composition.If make containing cementability rising agent in solidification compound, then the cementability between the cured film be made up of this solidification compound and the layer be adjacent improves, therefore preferably.Even be coated with the method for cementability rising agent on the layer that this is adjacent in advance, also cementability can be improved.
When in solidification compound of the present invention containing additive, its content is preferably 0.0001 ~ 30 quality %, is particularly preferably 0.0001 ~ 20 quality %.
(preferably combination of solidification compound)
Combination 1: the solidification compound be made up of following prepolymer (A), compound (B), liquid-repellant polymkeric substance (C) and thermal polymerization (D1).
Prepolymer (A): the prepolymer be made up of perfluorinated biphenyl, phloroglucinol and acetoxy-styrene.The content of the prepolymer (A) in solidification compound is 30 ~ 70 mass parts.
Compound (B): be selected from ethoxylation isocyanuric acid triacrylate, 6-caprolactone modification three-(2-acryloyl-oxyethyl) isocyanuric acid ester, 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, Viscoat 295, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, two (TriMethylolPropane(TMP)) tetraacrylate and Tricyclodecane Dimethanol diacrylate more than a kind.In the total (100 mass parts) of prepolymer (A) and compound (B), compound (B) is 20 ~ 60 mass parts.
Liquid-repellant polymkeric substance (C): the multipolymer with unit (u1) and unit (u2) using following (u1-1) ~ (u1-3) as unit (u1), use following (u2-1) as unit (u2), use following (u3-1) ~ (u3-7) as unit (u3), or there is the multipolymer of unit (u1), unit (u2) and unit (u3).The content of the liquid-repellant polymkeric substance (C) in solidification compound is 0.1 ~ 5 mass parts.
Thermal polymerization (D1): be selected from benzoyl peroxide and 2, more than a kind of 2 '-Diisopropyl azodicarboxylate.The content of the thermal polymerization (D1) in solidification compound is 1 ~ 15 mass parts.
Combination 2: the solidification compound be made up of following prepolymer (A), compound (B), liquid-repellant polymkeric substance (C) and Photoepolymerizationinitiater initiater (D2).
Prepolymer (A): the prepolymer be made up of perfluorinated biphenyl, phloroglucinol and acetoxy-styrene.The content of the prepolymer (A) in solidification compound is 30 ~ 70 mass parts.
Compound (B): be selected from ethoxylation isocyanuric acid triacrylate, 6-caprolactone modification three-(2-acryloyl-oxyethyl) isocyanuric acid ester, 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, Viscoat 295, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, two (TriMethylolPropane(TMP)) tetraacrylate and Tricyclodecane Dimethanol diacrylate more than a kind.In the total (100 mass parts) of prepolymer (A) and compound (B), compound (B) is 20 ~ 60 mass parts.
Liquid-repellant polymkeric substance (C): the multipolymer with unit (u1) and unit (u2) using following (u1-1) ~ (u1-3) as unit (u1), use following (u2-1) as unit (u2), use following (u3-1) ~ (u3-7) as unit (u3), or there is the multipolymer of unit (u1), unit (u2) and unit (u3).The content of the liquid-repellant polymkeric substance (C) in solidification compound is 0.1 ~ 5 mass parts.
Photoepolymerizationinitiater initiater (D2): be selected from IRGACUREOXE01 (Ciba Specialty Chemicals's system), IRGACUREOXE02 (Ciba Specialty Chemicals's system), IRGACURE369 (Ciba Specialty Chemicals's system), IRGACURE907 (Ciba Specialty Chemicals's system), more than a kind of DAROCURTPO (Ciba Specialty Chemicals's system).The content of the Photoepolymerizationinitiater initiater (D2) in solidification compound is 1 ~ 15 mass parts.
[coating composition]
Coating composition of the present invention comprises above-mentioned solidification compound and solvent (E).Coating composition this coating composition is coated substrate surface to form film, except desolventizing (E) from this film.Usually, the removing of solvent (E) is undertaken by making solvent (E) evaporate.Therefore, require that the boiling point of solvent (E) is lower than the boiling point of the composition beyond the solvent (E) in solidification compound.The compound normally compound (B) that above-mentioned (A) ~ (D) composition mid-boiling point is minimum, therefore, when solidification compound inclusion compound (B), the solvent (E) lower than the boiling point of this compound (B) is used.Otherwise, as compound (B), preferably use the compound with sufficiently high boiling point compared with solvent used (E).
As solvent (E), known solvent can be used.Ketones solvent, esters solvent, ether solvent, amide solvent, aromatic series kind solvent etc. can be exemplified, as concrete example, propylene glycol methyl ether acetate (hereinafter also referred to " PGMEA "), 1 can be exemplified, 3,5-Three methyl Benzene, N,N-dimethylacetamide, pimelinketone, tetrahydrofuran (THF) etc.
The content of the solvent (E) in coating composition is preferably 1 ~ 99.995 quality % in coating composition, is more preferably 30 ~ 99.99 quality %, is particularly preferably 50 ~ 90 quality %.
(preferably combination of coating composition)
As the combination that coating composition of the present invention is preferably following.
Combination 3: the coating composition be made up of preferably combination 1 and the following solvent (E) of above-mentioned solidification compound.
Solvent (E): be selected from more than a kind of PGMEA and pimelinketone.Content in coating composition is 50 ~ 90 quality %.
Combination 4: the coating composition be made up of the solvent (E) recorded in the preferably combination 2 of above-mentioned solidification compound and the preferably combination 3 of above-mentioned coating composition.
In addition, when solidification compound of the present invention is the solidification compound comprising prepolymer (A), compound (B), liquid-repellant polymkeric substance (C) and radical polymerization initiator (D), the heating by less than 250 DEG C (preferably less than 200 DEG C) is solidified fully.Therefore, can be use in the operation (low temperature process) of 250 DEG C in the higher limit of Heating temperature.In addition, excellent solvent resistance, low-k and the good cured film of the liquid-repellant on surface can be formed.
[there are the article of cured film]
The article with cured film of the present invention are the article of cured film having base material and at substrate surface, solidification compound of the present invention is solidified and obtain.
" at substrate surface, solidification compound of the present invention is solidified and the cured film that obtains " to be included in substrate surface directly form the form of cured film and form arbitrary layer at substrate surface, on this arbitrary layer, form both forms of cured film.
(base material)
As the material of base material, plastics, glass, silicon etc. can be exemplified.If use the plastics such as polycarbonate, polyethylene terephthalate, PEN, polyethersulfone, polyimide, then mechanical flexibility is excellent, therefore preferably.
(cured film)
The thickness of cured film suitably can set according to purposes, is generally about 0.1 ~ 100 μm, is preferably 0.2 ~ 50 μm.
[there is the manufacture method of the article of cured film]
The manufacture method with the article of cured film of the present invention is the method with following operation (I).
(I) be coated with coating composition of the present invention at substrate surface, except desolventizing (E), carry out heating or rayed and form the operation of cured film.
" be coated with coating composition of the present invention at substrate surface; except desolventizing (E), carry out heating or rayed and form cured film " be included in substrate surface and directly form the form of cured film and form arbitrary layer at substrate surface, form both forms of cured film on its surface.
When not using coating composition but use solidification compound, become following operation.
Be coated with solidification compound of the present invention at substrate surface and form film, carrying out heating or rayed and form the operation of cured film.
(operation (I))
As coating process, as long as the method that can form uniform film is just not particularly limited.Such as spin-coating method, obliterating (ワ イ プ コ ー ト) method, spraying method, scraper for coating method, dip coating, mould can be exemplified and be coated with method, ink jet method, flow coat method, rolling method, casting painting method, slot coated method, silk screen print method, Langmuir-Bu Luoer Ztel method, gravure coating process etc.Consider from productive viewpoint, preferred spin-coating method, ink jet method, slot coated method.
As the method for solvent (E) in removing film, known method can be exemplified, the method carrying out heating, the method for carrying out reducing pressure can be exemplified, carry out the method etc. that heats and reduce pressure.Not easily produce defect from the viewpoint of film, preferably carry out the method heated.Heating temperature is preferably 30 ~ 200 DEG C, is particularly preferably 40 ~ 150 DEG C.
When being cured (thermofixation) by heating, film is formed at substrate surface coating coating composition, carry out by the heating process (prebake) for the purpose of desolventizing (E), then carry out heating process (curing process), thus obtain cured film.When thermofixation, the heating process for solidifying can double as the heating process except desolventizing.
The Heating temperature of heating process (prebake) is preferably 40 ~ 200 DEG C, is particularly preferably 60 ~ 200 DEG C.
The Heating temperature of heating process (curing process) is preferably 100 ~ 200 DEG C, is particularly preferably 120 ~ 200 DEG C.
The heat-up time of heating process (prebake) is preferably 1 ~ 10 minute, is particularly preferably 1 ~ 5 minute.
The heat-up time of heating process (curing process) is preferably 1 ~ 10 minute, is particularly preferably 1 ~ 5 minute.
The temperature of the article of Heating temperature to be less than 200 DEG C be confession under directions heating is no more than 200 DEG C.In fact, the design temperature of the heating unit such as hot plate or stove is made to be less than 200 DEG C.
When being cured (photocuring) by rayed, film is formed at substrate surface coating coating composition, carry out by the heating process (prebake) for the purpose of desolventizing (E), then light (exposure) is irradiated, carry out heating process (curing process) as required, thus obtain cured film.
As long as the Photoepolymerizationinitiater initiater (D2) comprised in the light solidification compound irradiated to solidify has the light of the wavelength of sensitivity to it, be not particularly limited.Solidify light used normally ultraviolet (wavelength 200 ~ 400nm, preferably 300 ~ 400nm), but be not limited to this.Further, the side chain that had better not be used in the unit (u1) in liquid-repellant polymkeric substance (C) there is the light of the wavelength decomposed and the light of this wavelength had to the Photoepolymerizationinitiater initiater (D2) of sensitivity.
The Heating temperature of the heating process (prebake) when being cured by photocuring is preferably 30 ~ 100 DEG C, is particularly preferably 40 ~ 100 DEG C.
The Heating temperature of heating process (curing process) is preferably 60 ~ 200 DEG C, is particularly preferably 100 ~ 200 DEG C.
The heat-up time of heating process (prebake) is preferably 1 ~ 20 minute, is particularly preferably 1 ~ 10 minute.
The heat-up time of heating process (curing process) is preferably 1 ~ 20 minute, is particularly preferably 1 ~ 10 minute.
When carrying out the microfabrication based on photoetching, by optionally irradiating light (exposure) with photomask or laser apparatus, the part (exposure portion) of irradiation is solidified.Therefore, carry out after exposure develop (dissolved in unexposed portion and be scattered in solvent and the operation of removing), remove unexposed portion, the residual solvents of removing solidified portion, thus, obtains the cured film through microfabrication.As required, heating process (curing process) can be carried out after development.Now, residual solvents can be removed by this heating process (curing process).In addition, expose rear and heating steps (post exposure bake) can be carried out as required before development.
The Heating temperature of heating process (post exposure bake) is preferably 60 ~ 200 DEG C, is particularly preferably 100 ~ 200 DEG C.The heat-up time of heating process (post exposure bake) is preferably 1 ~ 20 minute, is particularly preferably 1 ~ 10 minute.
The manufacture method with the article of cured film of the present invention can have operation (II) after above-mentioned operation (I).By having operation (II), the pattern that can carry out lyophily region and liquid-repellant region is formed.
(II) to the cured film surface irradiation ultraviolet radiation partly obtained in above-mentioned operation (I), the operation on cured film surface with the article of the pattern in lyophily region and liquid-repellant region is obtained.
Below, the part of non-irradiation ultraviolet radiation is denoted as liquid-repellant region, the part lyophilised by uviolizing is denoted as lyophily region.
As forming the method for pattern be made up of lyophily region and liquid-repellant region, can exemplify cured film surface across the method for photomask irradiation ultraviolet radiation or the method to cured film surface laser apparatus optionally irradiation ultraviolet radiation.
As ultraviolet light source, the ultraviolet light source of the energy such as high voltage mercury lamp (i line 365nm), YAG laser (3 times of ripple 355nm) more than illumination wavelength 300nm can be used.Also can be lyophilised under the ultraviolet effect that cured film surface is less than 300nm at wavelength, therefore also can use and illumination wavelength can be less than the ultraviolet light source of 300nm.
After operation (II), the decomposition residue containing Cf base can be removed.Such as by heating or removing under vacuum.
[there are the article of functional film]
Of the present invention have in the article of the pattern in lyophily region and liquid-repellant region, can form functional film on the surface in lyophily region.
As the form of functional film, electrode (thin film transistor, organic EL), semiconductor layer (thin film transistor, organic EL), conductor layer (tellite, multilayer wired, touch-screen, solar cell), transistor material, resin layer etc. can be exemplified.Because cured film is insulativity, so preferred function film is the thin film transistor of electrode.
As semiconductor layer, organic semiconductor, oxide semiconductor, silicon semiconductor can be exemplified.
As resin layer, the heat-curing resins such as resol, urea-formaldehyde resin, melamine resin, acrylic resin, epoxy resin, urethane, polyester, silicone resin, polyimide or light-cured resin, prepolymer (A) etc. can be exemplified.
(OTFT)
Below, be described with reference to the example of accompanying drawing to OTFT.
As the form of functional film of the present invention, be not limited to following OTFT.
Fig. 1 is the sectional view of the example representing OTFT.
OTFT 10 comprises: base material 12; Be formed at the gate electrode 14 on base material 12 surface; The gate insulating film 16 (cured film) on cover gate electrode 14 and base material 12 surface; Optionally be formed at source electrode 18 and the drain electrode 20 (functional film) on gate insulating film 16 surface; Be formed at the organic semiconductor layer 22 on interelectrode gate insulating film 16 surface of source electrode 18 and drain electrode 20 and this.
As the material of base material 12, can exemplify above-mentioned materials, the preferred configuration of base material 12 is also identical.
Gate electrode 14, source electrode 18 and the electric level 20 that drains are formed by electrical conductor.As electrical conductor, can exemplify silicon, through doping silicon, platinum, gold and silver, copper, chromium, aluminium, calcium, barium, tin indium oxide, indium zinc oxide, zinc oxide, carbon black, fullerene, carbon nanotube, Polythiophene, polyethylene dioxythiophene, polystyrolsulfon acid, polyaniline, polypyrrole, polyfluorene etc.Electrical conductor can be used alone a kind, also can two or more also use.The material of gate electrode 14, source electrode 18 and the electric level 20 that drains can mutually the same also can be different.
The cured film that gate insulating film 16 obtains by making solidification compound of the present invention solidify at gate electrode 14 and base material 12 surface is formed.
The thickness (there is not the thickness t of the part of gate electrode 14) of gate insulating film 16 is preferably 1nm ~ 10 μm, is more preferably 2nm ~ 5 μm, is particularly preferably 5nm ~ 1 μm.If the thickness of gate insulating film 16 more than the lower value of above-mentioned scope, then not easily produces leakage current between gate electrode 14 and source electrode 18.If below the higher limit of above-mentioned scope, then driving voltage is inhibited.
As the material of organic semiconductor layer 22, known low molecular compound, oligopolymer, polymkeric substance etc. can be exemplified.
As low molecular compound, pentacene, rubrene, phthalocyanine, perylene, soccerballene, their derivative etc. can be exemplified.
As oligopolymer, oligothiophene, its derivative etc. can be exemplified.
As polymkeric substance, p-phenylene vinylene (PPV), polyfluorene, fluorenes-diazosulfide multipolymer, fluorenes-triphenylamine multipolymer, fluorenes-two thiophene copolymers, Polythiophene, polyaniline, polyacetylene, polypyrrole, their derivative etc. can be exemplified.
The thickness of organic semiconductor layer 22 is preferably 5nm ~ 100 μm, is more preferably 10nm ~ 10 μm, is particularly preferably 10nm ~ 1 μm.
In OTFT 10, the solidification compound of the application of the invention forms gate insulating film 16, and leakage current reduces.In addition, due to the filming of gate insulating film 16 can be realized, therefore can realize the miniaturization of element, the driving voltage of transistor can be reduced in addition.
In addition, in OTFT 10, surface due to gate insulating film 16 has good liquid-repellant, and the molecule therefore had in the organic semiconductor layer 22 be located on this gate insulating film 16 is easy to orientation, form the polar group of carrier top is difficult to be present in the not easily effect such as absorption such as the moisture in surface, air.Therefore, the electronic mobility in OTFT 10 uprises, and stability and reliability improve.
[there is the manufacture method of the article of functional film]
The manufacture method with the article of functional film of the present invention is the method with above-mentioned operation (I), (II) and following operation (III).
(III) after above-mentioned operation (II), at the surface optionally attached function film-forming composition of above-mentioned lyophily region (the illuminated ultraviolet part of cured film), thus the operation of functional film is formed.
Functional film formation composition is the composition (hereinafter also referred to " composition for electrodes, semiconductor layer composition, conductor layer composition, transistor material composition, resin layer formation composition ") forming electrode, semiconductor layer, conductor layer, transistor material, resin layer etc.
As functional film formation composition, such as, when functional film is electrode, the coating fluid of the precursor comprising above-mentioned electrical conductor or this electrical conductor can be exemplified.
" at the surface optionally attached function film-forming composition of above-mentioned lyophily region (the illuminated ultraviolet part of cured film), thus formed functional film " is included in cured film surface and optionally directly forms the form of functional film and optionally form arbitrary layer on cured film surface, form both forms of cured film on this arbitrary layer surface.
If formed with composition at the cured film surface coated functional film with the pattern be made up of lyophily region and liquid-repellant region, then functional film formation composition is optionally attached to lyophily region, is not attached to liquid-repellant region.Therefore, the functional film (electrode etc.) of predetermined pattern easily only can be formed in the lyophily region surface of cured film.As the method functional film formation that the lyophily region surface of cured film is adhered to composition being made functional film, known method can be adopted.
The surface in the liquid-repellant region of cured film of the present invention can also form functional film.Now, in order to improve the film-forming properties of functional film, to whole the exposure not having photomask, thus by lyophilised for liquid-repellant region, can then be coated with the functional film formation composition for the formation of functional film, forming functional film.
(manufacture method of OTFT)
Below, be described with reference to the example of accompanying drawing to the manufacture method of OTFT.
As long as the manufacture method of the present invention with the article of functional film has the method for above-mentioned operation (I) ~ (III), is not limited to the manufacture method of following OTFT.
Operation (I):
As shown in Figure 2, preparation surface is formed with the base material 12 of gate electrode 14.
As the formation method of gate electrode 14, sputtering, vacuum evaporation, spin coating, spraying, printing, ink-jet etc. can be exemplified.
Then, at gate electrode 14 and base material 12 surface coated coating composition of the present invention, except desolventizing (E), carry out heating or rayed, form gate insulating film 16 (cured film).Can think in gate insulating film 16, the structure deriving from prepolymer (A) concentrates on base material 12 side, and Cf base is present in the opposition side of base material 12 more.That is, the surface of gate insulating film 16 becomes the liquid-repellant region 16b with liquid-repellant.Symbol 16c in figure represents the interior region beyond the surface of gate insulating film 16.
Operation (II):
As shown in Figure 2, to the surperficial photomask of gate insulating film 16 (diagram slightly) or laser apparatus (diagram slightly) irradiation ultraviolet radiation (UV) partly, make the disengaging at least partially of the Cf base on gate insulating film 16 surface, form lyophily region 16a.Thus, the pattern be made up of lyophily region 16a and liquid-repellant region 16b is formed.Infer in gate insulating film 16, lyophily region 16a and liquid-repellant region 16b not with the clear and definite layering of interior region 16c under the top layer presenting these surface property, the concentration through-thickness consecutive variations of Cf base.
Operation (III):
If comprise the coating fluid of the precursor of electrical conductor or this electrical conductor in gate insulating film 16 (cured film) surface coated with the pattern be made up of lyophily region 16a and liquid-repellant region 16b, then coating fluid is optionally attached to lyophily region 16a, is not attached to liquid-repellant region 16b.Therefore, as shown in Figure 2, source electrode 18 and the drain electrode 20 of predetermined pattern easily only can be formed on the lyophily region 16a of gate insulating film 16.
As the coating process of coating fluid, ink-jet, divider, printing etc. can be exemplified.
Operation (IV):
As shown in Figure 3, at least to liquid-repellant region 16b irradiation ultraviolet radiation (UV) of the gate insulating film 16 between source electrode 18 and drain electrode 20, make the disengaging at least partially of the Cf base on gate insulating film 16 surface, change into lyophily region 16a.By interelectrode gate insulating film 16 surface conversion is become lyophily region 16a, following organic semiconductor layer composition can be coated the surface of interelectrode gate insulating film 16.
Operation (V):
As shown in Figure 3, at source electrode 18 and drain electrode 20 and this interelectrode gate insulating film 16 surface coated organic semiconductor layer composition, form organic semiconductor layer 22 by known methods such as heating.In addition, also can adopt first formed be made up of organic semi-conductor precursor layer, then by applying light or heat, this precursor conversion is become organic semi-conductor method.As precursor, silyl acetylene substituted pentacenes or four dicyclo porphyrins (テ ト ラ PVC シ Network ロ Port Le Off ィ リ Application) derivative can be exemplified.This precursor becomes pentacene or Tetrabenzoporphyrin derivative by thermal conversion.
Embodiment
Below, by embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiments.
Example 1 is synthesis example, and example 2 ~ 31 is embodiments.
(PGMEA contact angle)
The mensuration of the contact angle on cured film surface adopts consonance interface science Co., Ltd. (Association and interface science society) ProductName made: contact angle meter CA-A, is undertaken by sessile drop method under the condition of 25 DEG C.Cured film drips the PGMEA of about 1 μ L, measures contact angle.
[example 1]
(manufacture of prepolymer (A1-1))
Perfluorinated biphenyl (650g), 1 is dropped in 10L (liter) the glass four-hole boiling flask that Di Muluo cooling tube, thermocouple thermometer, mechanical stirrer are housed, 3,5-trihydroxybenzene (117g) and N,N-dimethylacetamide (hereinafter also referred to " DMAc ") (6202g).Stir while heat in oil bath, add rapidly sodium carbonate (575g) when liquid temperature reaches 60 DEG C.Continue to stir while in 60 DEG C of heating 24 hours.Then, stir and be cooled to 0 DEG C, add 4-acetoxy-styrene (200g) and potassium hydroxide (532g), after stirring 24 hours in 0 DEG C, be slowly added drop-wise to 5N aqueous hydrochloric acid and be about in 10L, carry out redeposition.After sedimentation and filtration, then use pure water 2 times.Then, at 60 DEG C, carry out vacuum-drying 12 hours, obtain prepolymer (A1-1) (800g) of white powder.The number-average molecular weight (Mn) of prepolymer (A-1) is 10000.
[example 2]
(manufacture of compound (m1-1))
Compound (a1-1) (Inc. of Ciba Specialty Chemicals, ProductName: IRGACURE2959) 2.5g and triethylamine 2.3g mixes and is dissolved in methylene dichloride 62mL, obtains solution.While by this solution in 0 DEG C of stirring, in this solution, drip the solution that acrylate chloride (compound (b1-1)) 1.0g is dissolved in methylene dichloride 8mL and obtains.After dropping terminates, stir 1 hour in 0 DEG C, obtain the solution of inclusion compound (c1-1).
While by the solution of inclusion compound (c1-1) in 0 DEG C of stirring, add triethylamine 1.7g.Then, 2-(seven fluorine propoxy-)-2,3,3,3-tetrafluoro propionyl fluorides (compound d1-1) 4.4g is dripped.After dropping terminates, in stirring at room temperature 1 hour, obtain the solution of inclusion compound (m1-1).
The solution of inclusion compound (m1-1) is injected frozen water, is extracted with ethyl acetate 3 times.Then, by organic layer dried over mgso, except desolventizing, residue carries out purifying by silica gel column chromatography (distillate uses ethyl acetate/hexane=1/2 (volumetric ratio)), thus obtains compound (m1-1) 2.0g.
The qualification of compound (m1-1) is passed through 1h-NMR and 19f-NMR carries out.
The NMR spectrum of compound (m1-1):
1h ?NMR (300.4MHz, solvent: CDCl 3, standard: TMS) δ (ppm): 1.85 (s, 6H), 4.27 (t, J=4.8,2H), 4.52 (t, J=4.8,2H), 5.87 (dd, J=10.5,10.8,1H), 6.16 (dd, J=10.5,17.1,1H), 6.45 (dd, J=17.1,17.4,1H), 6.92 (d, J=9.0,2H), 7.90 (d, J=9.0,2H).
19f ?NMR (282.7MHz, solvent: CDCl 3, standard: CFCl 3) δ (ppm) :-132.0 (m, 1F) ,-129.6 (m, 2F) ,-85.4 (m, 1F) ,-81.2 (m, 6F) ,-79.5 (m, 1F).
[changing 9]
[example 3]
(manufacture of liquid-repellant polymkeric substance (C-1))
In 2-butanone 2.0g, make compound (m1-1) 0.70g and methacrylic acid-2-hydroxy methacrylate 0.15g at n-dodecyl mercaptan 0.034g and 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile) (with Guang Chun medicine Co., Ltd. (with light Pure medicine society) system, ProductName: V-70) 0.005g existence under in 50 DEG C reaction 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.17g, dibutyl tin dilaurate 0.0007g and 2,6-ditertbutylparacresol 0.0084g, in 40 DEG C of reactions 24 hours, obtain the 2-butanone solution with the unit (u1-1) of following formula and the liquid-repellant polymkeric substance (C-1) of unit (u2-1).The 2-butanone solution of the liquid-repellant polymkeric substance (C-1) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-1) 0.75g.Oil repellent in liquid-repellant polymkeric substance (C-1) is 24.2 quality %, number-average molecular weight (Mn) is 8000.
[changing 10]
[example 4]
(manufacture of coating composition)
Using prepolymer (A1-1) 1.2g, dipentaerythritol acrylate (number-average molecular weight (Mn): 578) 0.8g, liquid-repellant polymkeric substance (C-1) 0.02g and the benzoyl peroxide 0.2g as thermal polymerization (D1) are dissolved in the PGMEA of 8.0g, make coating composition as compound (B).
[example 5]
(there is the manufacture of the article of cured film)
Make at glass baseplate (Corning Incorporated (コ ー ニ Application グ society), long × wide: 50mm × 50mm, thickness: 0.725mm) on per minute 1000 turns, the condition spin application composition of 30 seconds, heat 20 minutes with the hot plates of 150 DEG C, thus form the cured film of thickness 1 μm.
To cured film surface across mask pattern irradiation ultraviolet radiation (i line 365nm) partly.Ultraviolet irradiation uses the ProductName of SUSS Inc.: MA-8, illuminate condition is 100J/cm 2.Under this device and condition, can not the ultraviolet of below illumination wavelength 350nm.The PGMEA contact angle of illuminated ultraviolet part is less than 10 °, and the PGMEA contact angle of the part of non-irradiation ultraviolet radiation is 53 °.
[example 6]
(manufacture of compound (m1-2))
Except compound (b1-1) being changed into methacrylic chloride 1.2g, changing compound (d1-1) into 2, the fluoro-2-(1 of 2-bis-, 1,2, the fluoro-2-of 2-tetra-(pentafluoroethoxy) oxyethyl group) beyond acetylfluoride (compound (d1-2)) 4.6g, operate in the same manner as example 2, obtain compound (m1-2) 2.0g.
The qualification of compound (m1-2) is passed through 1h-NMR and 19f-NMR carries out.
The NMR spectrum of compound (m1-2):
1h ?NMR (300.4MHz, solvent: CDCl 3, standard: TMS) δ (ppm): 1.85 (s, 6H), 1.95 (s, 3H), 4.27 (t, J=4.8,2H), 4.52 (t, J=4.8,2H), 5.60 (s, 1H), 6.13 (s, 1H), 6.92 (d, J=8.7,2H), 7.92 (d, J=8.7,2H).
19f ?NMR (282.7MHz, solvent: CDCl 3, standard: CFCl 3) δ (ppm) :-88.9 (m, 4F) ,-88.7 (m, 2F) ,-87.1 (m, 3F) ,-78.5 (m, 2F).
[changing 11]
[example 7]
(manufacture of compound (m1-3))
Except compound (b1-1) being changed into methacrylic chloride 1.2g, changing compound (d1-1) into 2,3, the fluoro-2-of 3,3-tetra-(1,1,2,3,3,3-hexafluoro-2-(perfluor propoxy-) propoxy-) beyond propionyl fluoride (compound (d1-3)) 6.6g, operate in the same manner as example 2, obtain compound (m1-3) 3.5g.
The qualification of compound (m1-3) is passed through 1h-NMR and 19f-NMR carries out.
The NMR spectrum of compound (m1-3):
1h ?NMR (300.4MHz, solvent: CDCl 3, standard: TMS) δ (ppm): 1.85 (s, 6H), 1.95 (s, 3H), 4.27 (t, J=4.8,2H), 4.52 (t, J=4.8,2H), 5.60 (s, 1H), 6.13 (s, 1H), 6.92 (d, J=8.7,2H), 7.92 (d, J=8.7,2H).
19f ?NMR (282.7MHz, solvent: CDCl 3, standard: CFCl 3) δ (ppm) :-145.6 (m, 1F) ,-132.3 (m, 1F) ,-130.0 (m, 2F) ,-84.0 (m, 1F) ,-82.0 (m, 5F) ,-81.8 (m, 3F) ,-80.5 (m, 3F) ,-79.7 (m, 1F).
[changing 12]
[example 8]
(manufacture of liquid-repellant polymkeric substance (C-2))
In 2-butanone 2.3g, make compound (m1-2) 0.80g that obtains in example 6 and methacrylic acid-2-hydroxy methacrylate 0.17g at n-dodecyl mercaptan 0.037g and 2,2 '-azo two (2,4-methyl pentane nitrile) (with Guang Chun medicine Co., Ltd. system, ProductName: V-65) 0.005g existence under in 50 DEG C reaction 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.18g, dibutyl tin dilaurate 0.0007g and 2,6-ditertbutylparacresol 0.0091g, in 40 DEG C of reactions 24 hours, obtain the 2-butanone solution with the unit (u1-2) of following formula and the liquid-repellant polymkeric substance (C-2) of unit (u2-1).The 2-butanone solution of the liquid-repellant polymkeric substance (C-2) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-2) 0.87g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-2) are shown in table 1.
[changing 13]
[example 9 ~ 11]
(manufacture of liquid-repellant polymkeric substance (C-3) ~ (C-5))
Except incorporation is as shown in table 1, operate in the same manner as example 8, make pulverous liquid-repellant polymkeric substance (C-3) ~ (C-5).Oil repellent and the number-average molecular weight of gained liquid-repellant polymkeric substance are shown in table 1.
[example 12]
(manufacture of liquid-repellant polymkeric substance (C-6))
In 2-butanone 2.2g, make compound (m1-2) 0.80g, methacrylic acid-2-hydroxy methacrylate 0.03g and Octyl acrylate 0.04g under the existence of the V-65 of n-dodecyl mercaptan 0.031g and 0.004g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.09g, dibutyl tin dilaurate 0.0004g and 2,6-ditertbutylparacresol 0.0045g, in 40 DEG C of reactions 24 hours, obtain having the 2-butanone solution of the liquid-repellant polymkeric substance (C-6) of the unit (u1-2) of following formula, unit (u2-1) and unit (u3-1).The 2-butanone solution of the liquid-repellant polymkeric substance (C-6) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-6) 0.72g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-6) are shown in table 1.
[changing 14]
[example 13 ~ 15]
(manufacture of liquid-repellant polymkeric substance (C-7) ~ (C-9))
Except incorporation is as shown in table 1, operate in the same manner as example 12, make pulverous liquid-repellant polymkeric substance (C-7) ~ (C-9).Oil repellent and the number-average molecular weight of gained liquid-repellant polymkeric substance are shown in table 1.
[example 16]
(manufacture of liquid-repellant polymkeric substance (C-10))
In 2-butanone 2.4g, make compound (m1-2) 0.90g, methacrylic acid-2-hydroxy methacrylate 0.03g and vinylbenzene 0.08g under the existence of the V-65 of n-dodecyl mercaptan 0.035g and 0.005g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.03g, dibutyl tin dilaurate 0.0001g and 2,6-ditertbutylparacresol 0.0017g, in 40 DEG C of reactions 24 hours, obtain having the 2-butanone solution of the liquid-repellant polymkeric substance (C-10) of the unit (u1-2) of following formula, unit (u2-1) and unit (u3-2).The 2-butanone solution of the liquid-repellant polymkeric substance (C-10) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-10) 0.44g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-10) are shown in table 1.
[changing 15]
[example 17]
(manufacture of liquid-repellant polymkeric substance (C-11))
Except incorporation is as shown in table 1, operate in the same manner as example 16, make pulverous liquid-repellant polymkeric substance (C-11).Oil repellent and the number-average molecular weight of gained liquid-repellant polymkeric substance are shown in table 1.
[example 18]
(manufacture of liquid-repellant polymkeric substance (C-12))
In 2-butanone 2.8g, make compound (m1-2) 1.00g, methacrylic acid-2-hydroxy methacrylate 0.04g and N-Hexyl methacrylate 0.14g under the existence of the V-65 of n-dodecyl mercaptan 0.039g and 0.005g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.04g, dibutyl tin dilaurate 0.0002g and 2,6-ditertbutylparacresol 0.0019g, in 40 DEG C of reactions 24 hours, obtain having the 2-butanone solution of the liquid-repellant polymkeric substance (C-12) of the unit (u1-2) of following formula, unit (u2-1) and unit (u3-3).The 2-butanone solution of the liquid-repellant polymkeric substance (C-12) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-12) 0.88g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-12) are shown in table 1.
[changing 16]
[example 19]
(manufacture of liquid-repellant polymkeric substance (C-13))
Except incorporation is as shown in table 1, operate in the same manner as example 18, make pulverous liquid-repellant polymkeric substance (C-13).Oil repellent and the number-average molecular weight of gained liquid-repellant polymkeric substance are shown in table 1.
[example 20]
(manufacture of liquid-repellant polymkeric substance (C-14))
In 2-butanone 2.6g, make compound (m1-2) 0.90g, methacrylic acid-2-hydroxy methacrylate 0.03g and lauryl methacrylate 0.18g under the existence of the V-65 of n-dodecyl mercaptan 0.035g and 0.005g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.03g, dibutyl tin dilaurate 0.0001g and 2,6-ditertbutylparacresol 0.0017g, in 40 DEG C of reactions 24 hours, obtain having the 2-butanone solution of the liquid-repellant polymkeric substance (C-14) of the unit (u1-2) of following formula, unit (u2-1) and unit (u3-4).The 2-butanone solution of the liquid-repellant polymkeric substance (C-14) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-14) 0.72g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-14) are shown in table 2.
[changing 17]
[example 21]
(manufacture of liquid-repellant polymkeric substance (C-15))
Except incorporation is as shown in table 1, operate in the same manner as example 20, make pulverous liquid-repellant polymkeric substance (C-15).Oil repellent and the number-average molecular weight of gained liquid-repellant polymkeric substance are shown in table 2.
[example 22]
(manufacture of liquid-repellant polymkeric substance (C-16))
In 2-butanone 2.7g, make compound (m1-2) 1.00g, methacrylic acid-2-hydroxy methacrylate 0.04g and methyl methacrylate 0.08g under the existence of the V-65 of n-dodecyl mercaptan 0.039g and 0.005g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.04g, dibutyl tin dilaurate 0.0002g and 2,6-ditertbutylparacresol 0.0019g, in 40 DEG C of reactions 24 hours, obtain having the 2-butanone solution of the liquid-repellant polymkeric substance (C-16) of the unit (u1-2) of following formula, unit (u2-1) and unit (u3-5).The 2-butanone solution of the liquid-repellant polymkeric substance (C-16) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-16) 0.72g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-16) are shown in table 2.
[changing 18]
[example 23]
(manufacture of liquid-repellant polymkeric substance (C-17))
Except incorporation is as shown in table 1, operate in the same manner as example 22, make pulverous liquid-repellant polymkeric substance (C-17).Oil repellent and the number-average molecular weight of gained liquid-repellant polymkeric substance are shown in table 2.
[example 24]
(manufacture of liquid-repellant polymkeric substance (C-18))
In 2-butanone 2.7g, make compound (m1-2) 1.00g, methacrylic acid-2-hydroxy methacrylate 0.04g and butyl methacrylate 0.11g under the existence of the V-65 of n-dodecyl mercaptan 0.039g and 0.005g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.04g, dibutyl tin dilaurate 0.0002g and 2,6-ditertbutylparacresol 0.0019g, in 40 DEG C of reactions 24 hours, obtain having the 2-butanone solution of the liquid-repellant polymkeric substance (C-18) of the unit (u1-2) of following formula, unit (u2-1) and unit (u3-6).The 2-butanone solution of the liquid-repellant polymkeric substance (C-18) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-18) 0.91g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-18) are shown in table 2.
[changing 19]
[example 25]
(manufacture of liquid-repellant polymkeric substance (C-19))
In 2-butanone 2.5g, make compound (m1-2) 0.80g, methacrylic acid-2-hydroxy methacrylate 0.03g and RUVA-93 (trade(brand)name ， Otsuka Chemical Co., Ltd system) 0.21g under the existence of the V-65 of n-dodecyl mercaptan 0.031g and 0.004g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.03g, dibutyl tin dilaurate 0.0001g and 2,6-ditertbutylparacresol 0.0015g, in 40 DEG C of reactions 24 hours, obtain having the 2-butanone solution of the liquid-repellant polymkeric substance (C-19) of the unit (u1-2) of following formula, unit (u2-1) and unit (u3-7).The 2-butanone solution of the liquid-repellant polymkeric substance (C-19) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-19) 0.66g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-19) are shown in table 2.
[changing 20]
[example 26]
(manufacture of liquid-repellant polymkeric substance (C-20))
In 2-butanone 2.2g, make compound (m1-3) 0.80g that obtains in example 7 and methacrylic acid-2-hydroxy methacrylate 0.14g under the existence of the V-65 of n-dodecyl mercaptan 0.030g and 0.004g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.15g, dibutyl tin dilaurate 0.0006g and 2,6-ditertbutylparacresol 0.0073g, in 40 DEG C of reactions 24 hours, obtain the 2-butanone solution with the unit (u1-3) of following formula and the liquid-repellant polymkeric substance (C-20) of unit (u2-1).The 2-butanone solution of the liquid-repellant polymkeric substance (C-20) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-20) 0.76g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-20) are shown in table 2.
[changing 21]
[example 27 ~ 29]
(manufacture of liquid-repellant polymkeric substance (C-21) ~ (C-23))
Except incorporation is as shown in table 1, operate in the same manner as example 26, make pulverous liquid-repellant polymkeric substance (C-21) ~ (C-23).Oil repellent and the number-average molecular weight of gained liquid-repellant polymkeric substance are shown in table 2.
[example 30]
(manufacture of liquid-repellant polymkeric substance (C-24))
In 2-butanone 2.6g, make compound (m1-3) 0.80g, methacrylic acid-2-hydroxy methacrylate 0.03g and Octyl acrylate 0.24g under the existence of the V-65 of n-dodecyl mercaptan 0.037g and 0.005g in 50 DEG C of reactions 24 hours.After being cooled to room temperature (20 ~ 25 DEG C), add 2-acryloyloxyethyl isocyanate 0.04g, dibutyl tin dilaurate 0.0001g and 2,6-ditertbutylparacresol 0.0018g, in 40 DEG C of reactions 24 hours, obtain having the 2-butanone solution of the liquid-repellant polymkeric substance (C-24) of the unit (u1-3) of following formula, unit (u2-1) and unit (u3-1).The 2-butanone solution of the liquid-repellant polymkeric substance (C-24) of gained is dropped into hexane makes it precipitate, and by the vacuum-drying of gained solid, obtains pulverous liquid-repellant polymkeric substance (C-24) 0.57g.Oil repellent and the number-average molecular weight of liquid-repellant polymkeric substance (C-24) are shown in table 2.
[changing 22]
[example 31]
(manufacture of liquid-repellant polymkeric substance (C-25))
Except incorporation is as shown in table 1, operate in the same manner as example 24, make pulverous liquid-repellant polymkeric substance (C-25).Oil repellent and the number-average molecular weight of gained liquid-repellant polymkeric substance are shown in table 2.
[table 1]
[table 2]
The possibility that industry utilizes
Solidification compound of the present invention can have the article of the pattern in lyophily region and liquid-repellant region for the formation of the cured film surface at gained easily, useful as the electrical insulating film in various electronic component (semiconductor element etc.) etc., chemistry or physical protection film, non-tack film etc.Specifically, flexible equipment interlayer dielectric can be used as, the protective membrane of flexible equipment, the gate insulating film of OTFT, the gate insulating film of oxide thin film transistor, capacitor insulating film, the gate insulating film of internal memory transistor, the passive film of semi-conductor, the protective membrane of semiconductor element, the multilayer wired interlayer dielectric of high-density installation, the insulating film of organic electroluminescent device, distribution insulating film again, the tectum of flexible copper-clad plate, soldering-resistance layer, liquid crystal orientation film, colour filter protective membrane, the resin terminal (Trees fat Port ス ト) of semiconductor element etc., the spaced walls etc. of colour filter etc.
Here the announcement of full content as specification sheets of the present invention of the specification sheets of No. 2011-274320, the Japanese patent application that on December 15th, 2011 files an application, claims, accompanying drawing and summary is quoted.
The explanation of symbol
10 OTFT
12 base materials
14 gate electrodes
16 gate insulating films
16a lyophily region
16b liquid-repellant region
16c interior region
18 source electrodes
20 drain electrodes
22 organic semiconductor layers

Claims (15)

1. the liquid-repellant compound that represents of following formula (m1);
[changing 1]
Wherein,
Cf is the fluoro-alkyl between the fluoro-alkyl of carbon number 1 ~ 20 or carbon atom with the carbon number 1 ~ 20 of etheric oxygen atom;
R 1and R 2it is separately the alkyl of carbon number 1 ~ 6;
X is Sauerstoffatom;
N is 1;
M is 1;
Z is R 4r 5c=CR 3-CO-;
R 3, R 4and R 5be separately hydrogen atom or methyl.
2. liquid-repellant polymkeric substance, is characterized in that, has the unit based on liquid-repellant compound according to claim 1.
3. liquid-repellant polymkeric substance as claimed in claim 2, is characterized in that, also comprises and has cross-linking functional group and the unit not containing Cf base.
4. solidification compound, is characterized in that, comprises the liquid-repellant polymkeric substance described in Claims 2 or 3.
5. solidification compound as claimed in claim 4, is characterized in that, also comprise radical polymerization initiator.
6. the solidification compound as described in claim 4 or 5, is characterized in that, also comprises the fluorine-containing polyarylene prepolymer with cross-linking functional group.
7. solidification compound as claimed in claim 6, is characterized in that, also comprises that number-average molecular weight is 140 ~ 5000, the compound with cross-linking functional group, non-contain fluorine atoms.
8. solidification compound as claimed in claim 6, it is characterized in that, described fluorine-containing polyarylene prepolymer be make to have cross-linking functional group and phenolic hydroxyl group compound and there is either one or both in the compound of cross-linking functional group and fluorine atom substituted aroma ring, compound (y) that following formula (y) represents, the compound with more than 3 phenolic hydroxyl group under the existence of dehydrohalogenating agent, carry out condensation reaction and obtain, the prepolymer with cross-linking functional group and ehter bond;
[changing 2]
Wherein, a is the integer of 0 ~ 3, and b is the integer of 0 ~ 3, and c is the integer of 0 ~ 3;
Rf 1and Rf 2be separately the fluoro-alkyl of carbon number less than 8, the F in aromatic nucleus represents that the hydrogen atom of this aromatic nucleus is all replaced by fluorine atoms.
9. coating composition, is characterized in that, comprises the solidification compound according to any one of claim 4 ~ 8 and solvent.
10. article, is characterized in that, the cured film having base material and at substrate surface, the solidification compound according to any one of claim 4 ~ 8 is solidified and obtain.
11. article, it is the article on cured film surface with the pattern in lyophily region and liquid-repellant region, and it is characterized in that, the cured film that this liquid-repellant region is solidified by the solidification compound made according to any one of claim 4 ~ 8 and obtained is formed.
12. have the manufacture method of the article of the pattern in lyophily region and liquid-repellant region on cured film surface, it is characterized in that, comprise following operation (I) ~ (II):
(I) be coated with coating composition according to claim 9 at substrate surface, except desolventizing, carry out heating or rayed and form the operation of cured film;
(II) to described cured film surface irradiation ultraviolet radiation partly, the operation on cured film surface with the article of the pattern in lyophily region and liquid-repellant region is obtained.
The manufacture method of 13. article as claimed in claim 12, is characterized in that, also comprise following operation (III) after described operation (II):
(III) optionally adhere in described lyophily region surface more than one that be selected from composition for electrodes, semiconductor layer composition, conductor layer composition, transistor material composition and resin layer composition, form more than one the operation being selected from electrode, semiconductor layer, conductor layer, transistor material and resin layer.
14. article as claimed in claim 11, is characterized in that, are also formed with in described lyophily region surface more than one that be selected from electrode, semiconductor layer, conductor layer, transistor material and resin layer.
15. article as claimed in claim 14, it is characterized in that, described article are thin film transistors.
CN201280061108.0A 2011-12-15 2012-12-13 Liquid-repellant compound, polymkeric substance, composition, article and manufacture method thereof Expired - Fee Related CN103998414B (en)

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